CA1274048A - Bismaleimide formulations containing olefinic ether modifiers - Google Patents
Bismaleimide formulations containing olefinic ether modifiersInfo
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- CA1274048A CA1274048A CA000534639A CA534639A CA1274048A CA 1274048 A CA1274048 A CA 1274048A CA 000534639 A CA000534639 A CA 000534639A CA 534639 A CA534639 A CA 534639A CA 1274048 A CA1274048 A CA 1274048A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/408—Imides, e.g. cyclic imides substituted imides comprising other heteroatoms
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
Abstract
Bismaleimide Formulations Containing Olefinic Ether Modifiers ABSTRACT OF THE DISCLOSURE
Novel bismaleimide resin formulations are described which contain olefinic ether reactive diluents. These formulations provide a combination of prepreg processing characteristics and thermal and mechanical properties unavailable from other reactive diluents. Preferred diluents contain one or more ally ether groups.
Novel bismaleimide resin formulations are described which contain olefinic ether reactive diluents. These formulations provide a combination of prepreg processing characteristics and thermal and mechanical properties unavailable from other reactive diluents. Preferred diluents contain one or more ally ether groups.
Description
~. ~}7~
BISMALEIMIDE FO~MULATIONS
CONTAINING OLEFINIC ETHER
MODIFIERS
FIELD OF THE INVENTION
Thls inven~lon relet~s to novel bismaleimlde formul~tions cont~ining olefinic ether d~luents. In p~rticulsr, lt rel~tes to the use of liquid reactlve dlluents contRinlng one o~ ~ore allyl ether groups to provlde bismalelmide formulations hQvlng a deslrable balance of properties. In a further aspect, ~he present lnvention relates to the use of these novel bismaleimide formulstions ln the prepar~lon of prepreg resins for tape or tow fabrication snd the compos1tes prepared therefrom.
ACKGROUND OF THE INVENTION
Adv~nced composi~es are high strength, high modulus m~terials which ~re finding increasin~ use ~s structural components in ~ircr~ft, automotlve, ~nd sportlng goods ~ppllca~iorls. Typically, they comprlse structural fibers sueh ~s c~rbon fi~ers in the form of woven cloth or contlnuous f1laments embedded ln a thermose~lng resin m~trix.
Most adv~nced composites ~re f~bricat~d from prepreg, a ready-to-mold sheet of relnforcement impregnated with uncured or pRrtlslly cured resln.
Resin systems containing ~n epoxide resin ~nd ~romatlc emine hflrdener ~re often used ln prepre~
slnce they possess the bal~nce of propertles requlred for this composlte f~bricatlon process.
, ':
-:"' : -~. ' 7f~ 3
BISMALEIMIDE FO~MULATIONS
CONTAINING OLEFINIC ETHER
MODIFIERS
FIELD OF THE INVENTION
Thls inven~lon relet~s to novel bismaleimlde formul~tions cont~ining olefinic ether d~luents. In p~rticulsr, lt rel~tes to the use of liquid reactlve dlluents contRinlng one o~ ~ore allyl ether groups to provlde bismalelmide formulations hQvlng a deslrable balance of properties. In a further aspect, ~he present lnvention relates to the use of these novel bismaleimide formulstions ln the prepar~lon of prepreg resins for tape or tow fabrication snd the compos1tes prepared therefrom.
ACKGROUND OF THE INVENTION
Adv~nced composi~es are high strength, high modulus m~terials which ~re finding increasin~ use ~s structural components in ~ircr~ft, automotlve, ~nd sportlng goods ~ppllca~iorls. Typically, they comprlse structural fibers sueh ~s c~rbon fi~ers in the form of woven cloth or contlnuous f1laments embedded ln a thermose~lng resin m~trix.
Most adv~nced composites ~re f~bricat~d from prepreg, a ready-to-mold sheet of relnforcement impregnated with uncured or pRrtlslly cured resln.
Resin systems containing ~n epoxide resin ~nd ~romatlc emine hflrdener ~re often used ln prepre~
slnce they possess the bal~nce of propertles requlred for this composlte f~bricatlon process.
, ':
-:"' : -~. ' 7f~ 3
- 2 St~te-of-the-~rt epoxy/carbon fiber composltes h~ve hi~h compressive Qtrength~, ~ood f~tigue ch~racterlsties, ~nd low shrlnkhKe dur~n~ cu~e.
However, ~ost epoxy formul~tions ~bsorb molsture whlch reduces their high temperQture properties. A~
~ result, they sre not suitable ~or use ~t 300DF or grester ~n ~ moisture ~turQted condition. There is therefore a need for ~esin systems which ~fford composites which csn retsln ~ high level of properties at 300F under such ~oisture ~turated conditions.
Most prepre~ resins designed for use at temperatures of 300F or higher ~re m~de by comblnlng bismaleimldes of Formul~ I with liquid coresct~nts containing other reactive groups such as ~mines, epoxldes, cysnstes or comonomers contslnlng -CH-CH2,~C=CH2, or -CH=CH- groups which can reac~ or polymerlze with the csrbon-cRrbon double bonds of the m~leimide groups.
N-~-O O
In the most common blsmsleimides, R is the resldue of ~n Rrom~tic diamine ~uch 8S methylene di~nlllne or rel~ted derlvatlves.
A wlde r~nge of blsmalelmlde comp~sltions based on dlfferlng ~romatic residues or blcnds of ~'7~
bismsleimides c~n be used, however. All of these bismaleimldes ~re sollds or glas~es at room temper~ture which requlre ll~uld coreact~nts ~n order to provide ~ processible ~nd useful resln ~or composite fAbricstlon.
The range o ~ultable llquid reactlve dlluents containing uns~turfited c~rbon-c~rbon double bonds, however, is ourrently very limited. M~ny of the ~v~ ble diluents ~re restricted by thetr lcw bolling points snd, therefore, hi~h volatility; by their odor; by their toxlclty ~ndtor problems with ~kin irrit~tion; by their poor ~bllity to dissolve bismelelmides; by their high viscosity which, s~in, limits the bismsleimlde solubllity ~nd ~lso le~ds to llttle or no tack in the formulation; by thelr poor th~rmsl st~billty or hydrolytic stabllity; by their lncompatibll1ty wlth othe~ formuls~lon modifiers; by their effect on the mechanlc,~l properties of the cured f~rmulation; ~nd/or by their tendency to c~use rapid cross-linking ~nd gellation of the bismaleimide formulation.
A need cle~rly exlsts, therefore, for new and effective reactlve dlluents which can overcome all or at lesst ~any of the ~bove noted problems.
SUMMARY OF THE_INVENTION
Applicsnt has discovered new blsmaleimide formul~tions contain1ng liquid reactive dlluen~s which Avoid substan~lally all of the cbove-noted dlssdv~nt~ges commonly sssoclste~ wlth the prior ~rt diluents.
More p~rtlcul~rly, ApplicQnt has discovered thst oleflnlc ethers and especi~lly allyl ethers c~n . ~
~" ~
~ct ~s dlluents for blsm~leimide for~ul~lon~ to provlde cured products wl th low water Qb~orption ~nd ~ wide range of glass trsnsltion temperatures ~Tg).
T8 velues of 350C and hi~her c~n be obtQined dependlng on the p~rtlcul~r ~ormul~tion.
An ~ddltion~l ~dv~nt~ge of the olefinlc ether/bism~lelmlde formulatlons ~ 8 their ~bility to B-~t~ge or ~dvance low v15~0sity formulat~ons to deslred vlscoslty sultsble, for example, for prepre~
tow or tspe f~brlc~tion. Unllke general ~ree-r~dlcal curlng resins, these formul~tions show a gradu~l lncre~se in viscoslty wlthout fiigns of gell~tion or ~n ebrupt exotherm. This fe~ture i~
useful ln optimizing a given formul~tion for u~e in specific composlte fsbricatlon technlques.
Moreover, unlike other dlluents such ~s divinylbenzene, oleflnlc ether reactive dlluents provlde 800d stablllty ln the uncured resin ~nd h~ve little or no odor. Addi~lonally, unllke m~ny low viscosity diluents such ~s st:yrene, the diluents of the present invention h~ve low volstllity ~t ~mbient temperatures.
In contrAst to other commonly ~v~llable sllyl dlluents such as disllyl phthal~te ~nd tri~llylisocysnur~te, the diluents o~ thls invention provide enhanced Tg v~lues ~nd/or mechanic~l propertles.
Still further, unlike diluen~s whlch cont~in resldu~l phenolic, hydroxyl, or other actlve hydro~en groups, the diluents of the present inventlon c~n be used ln con~unction wlth cy~n~te ester resins without premature gellatlon.
5 ..
.
So too, ln contr~st to diluents cont~inlng multlple ester bonds, ~he oleflnlc e~her dlluents of ~he present inventi~n provlde excellent ~her~al ~nd hydrolytic ~tability.
Fin~lly, unlike acryllc or methscryllc diluents, the diluents of the pre ent invention gener~lly do not ~ppear to cQuse skin sensitlvity or other toxlcity problems.
Speciflc~lly, the new resin formulations of the present invention comprise:
(l) bi~m~leimide; ~nd (li) st least one or more of 8 re~otlve diluent which may be descrlbed by the following general formulc:
II ~R3m EAr~ ZR3n where Z = O or S, snd where R ~ -CH'CH2, -CH2CH=CH2, -CH -C CH~, CH
-CH=CHCH3.
C~
- C ~ /
~2~ ~
r~ b~
~ C ~
--C~ C'~
~ z~
n > 1, m = 0 to 2, m ~ n ~ 2 Ar c ~ ~
~X~
in which X = ~lkylldene, Rryl, arylalkylldene, r S~ S02~ GO~
O O
- C - O -, - C - NH-, -O(CH2)nO-and where Ar msy option~lly be ~ubstltuted with ~lkyl, alkoxy, halogen, and other non-reactlve groups.
These formulstions msy optlonRlly cDnt~ln ~dditives such ~s thermopl~stlcs, epoxy reslns, am1ne hardeners, cyanete res~ns, filler6 or other modiflers ~nd may also contaln 8 ~tructus~l f~ber.
DETAILED DESCRIPTIO~ OF THE INVENTION
The allyl Qnd methallyl dtluents of thls lnvPntion are reQdlly prepared from ~v~ ble ~henol~c msterials ~nd ~llyllc h~lides. Numerous ~olvents including ~lcohols, ethers And dipol~r ~protic solvents such as dimethyl ~ormamlde, dlmethyl ~cet~mlde snd dlmethyl sulf~xide ~ay be , :' ' -:
~ ~ 7 L~ ~ L?~
used ~s ~ell ~s both hydroxlde ~nd csrbon~te b~es.
Propenyl ether~ msy be prep~red by b~se-c~talyzed lsomeri~tlon of the allyl ~thers. Methcds ~or the prep~r~tlon of ~lnyl ~thers ~re well known to ~hose ~kllled ln the art.
Preferred diluents inolude the followlng ~tructures:
~0 ~ o-cH2o~2 III
CH2=CH-CH ~
CH2=CHCH2-0 ~ l, ~ -CH2o~2 IV
lC:H2=CHCH~-O ~ CK ~2a ~ 2 V
CH2=CHCH2-o ~ o-CH2~o~2 VI
~-lS180 ~lX7~ 8 ,~ ~CH2CH~H2 V I I
CH2~H-CH2 CH2=CHcH2 ~cH2cH~H2 VI I I
~C H2CH5CH2 ~CH2~H=CH2 ~2-( H~2 X
2~ 2 ~12~1~2 CH2=CHCH2-O ~J o CH2CH=CH2 X I
o-CH2CH~CH2 .., . ~ .
., '~ .
7~ 8 CH2=cHC:H2~ ~cH2cH=cH2 XI I
,~ ~c H2~H~H2 X I 1 I
CH3 O-cH2CH=CH2 OCH
H2c H~H2 X I V
O-CH2CH~H2 ~2~2~(~2)~0-C~2CH--CH2 XV
n ~ 1-6 In all of the above structures, it ls posslble to substltu~e vlnyl ether, propenyl ether , .:
or meth~llyl ether groups for the ellyl ether ~roups æhow. Allyl ethers ~re ~he preferred oleflnlc ethers.
Additional ~terlQls whlch fsll under the bro~d ~cope of thi~ lnventlon ~re ~hose ol~flnlc ethers whlch ~re ~olld ~t ~bient temper~ture but whlch m~y be used ~s blends with other liqu~d diluen~s. Preferred ex~mples of these coreact~nts lnclude the diAllyl ether of biphenol, o bisphenol S, snd of naphth~lene diol 8S shown below:
CH2=CHCH2-o ~ o-cH2cH=cH2 XVI
O-CH2CH=CH2 5~ XV I I
0-CH 2CH=CH 2 C}12=CHCH2-0~ so24~ 0-CH2CH=CH2 XYI I I
74~L~ ~3 The bismalelmides ~ult~ble for use ln the formul~lons of this ~nvention ~re defined by structure I where R c~n be the resldue of an uromstlc or ~llphatic organlc comp~und. Preferr~d blsm~leimides include the following s~ructures wh~ch may be u~ed ~lone or 8S ~ixtures:
\,~C~3 ~ \ 3 CH~ Ic 3 ~ ~5~80 ~7~
~, ~0~ ' 3 CH3 C~ O
N~ N 3 o U o N~O~ 0~ N 3 o o o o ~ ~\`~S2 ~ ~C 3 o o o O O
,, o c ~ ~ ~ ~c 3 , ~ 3 .. . . .
~74~
o o ~ c~ C~ 3 o E~ c~ C 3 o , ~C~/ ~
~c~ 3 o o o o :'". ' :, .: ::,. :
~ ~ 7 ~
Il ~
C ~ C
O O
CH3 c ~C ~ ~
¢ lNC~2 1CCH2CHCH2CH N/ 3 CH~ ,RI~ C ~--CH,~ ~ 3 ~ where ~ ls the r~sldue of ~n ~romatlc dl~mine or ~mlnohydrazlde.) ''. ' - . :....
.'''", ~. .
1~74~3~
~ ther bismsleimides not speclfically shown Qbove may ~l~o be used in ~he present lnventi3n. It ~s ~lso po~slble to use bism~leimides ln ~hieh up to 50~ of ~he malelmlde groups have been repl~ced by ~ubstituted malelmide groups ~uch as methyl malemldes or hAlomale~mldes or by the n~dimlde, methyl nadimlde, or i~omaleimide groups ~hown below:
~/ 3 ~ T
~~ ,. a _x-~c~ c8~
where T = methyl, hslogen, hydro~en.
Portions of ~he mslemlde groups m~y ~lso be replaced by succintmide, phthsllmide, or ~ubstlt~ted succlnlmlde ~nd phthallmide ~roups.
An ~dvantag2 of cert~ln of the formulations of this inventlon ls thelr ~bility to be controllsbly "B-staged" or increas2d ln vlscoslty wlthout the common prob~em of Qell6tlon which ls assocl~ted w1th m~ny reactlve dlluents. In p~rtlcul~r, blends of the ~llyl ether of Eugenol (III) wlth Compimlde 353 (~ commerclslly ~v~ ble mixture of blsmaleimides obt~ined from Boots-Technochemle, Nottlngham, Engl~nd) pr~vide s very low viscosity resin (< 180 cps) at room temper~ture whlch is sultable for ln~ectlon into preformed msts of relnforclng flbers. ~dvsncement of thi~ resin ~t elev~ted temperatures ~uch OQ 120 - 150C can be c~rrled out to provlde a ~lmllsr resin of hl~her vi~coslty whlch ls ~uitHble for wet-wlndln~ or prepreg tow f~bric~tion. Gon~inued ~dvancement cRn be c~rrled out ~o prov~de ~ ~e~ln vi~coslty suitQble ~or film-eoating and prepreg tape febrle~tlon.
The low vlsco~ity of ~his and ~lmil~r resins c~n al~o be ad~u~ted by the addltion of thermop~stlc polymers, particulate fillers, ~nd other conventional resln sdditlves.
In addition to the blsmaleimides ~nd olefinic ether dlluents used in the formul~tions of the present lnvention, other reactive dlluent~ and modiflers m~y be lncluded ln the formulatlons.
Li~uid re~ctlve diluen~s which can be used as modifiers include N-vlnyl-2-pyrrolidin~ne, N-vlnyl csprol~ctsm, ethylene glycol dimeth~crylate, dlethylene glycol dimethacrylste, ethoxyl~ted bisphenol A dimethacryl~te, trlmethylolpropane tri~crylate, trimethylolpro1?ane trlmethacryl~te, pentserythri~ol triacrylate, pentaerythri~ol tetra~cryl~te, pent~erythrltol tetramethflcrylate, trl~llyl lsocy~nurate, trlAllyl cydnurste, di~llyl phthal~te ~nd its ifiomers, tetra~llyl pyromellltate, o,o'-dlallyl bisphenol A, Eugenol, trl~llyl trimellitste, divlnyl benzene, d~cyclopen~adienyl ecryls~e, dicyclopentadlenyloxyethyl acryl~te, v~nylcyclohexene monoepoxlde, 1,4-but~nediol divinyl ether, 1,4-dlhydroxy-2-butene, styrene, slpha methyl styrene, chlorostyrene, p-phenylstyrene, p-me~hylstyrene, t-butylstyrene, phenyl vlnyl ether, uns~tursted polyesters, vinyl ester resin~, ~nd ehe like. These comonomer~ ~re chQr~c~erized by the presence of one or more -CH~CH2,,G'CH2, or -C~CH- groups which c~n polymerlze or ~eact wlth the malelmlde groups of the bl~m~leimide.
Other llquld core~c~ants ~nclude epoxy resins whieh contain one or more epoxy ~roup~ havln~ -the following formul~:
o ~ ~ g_ The epoxy groups can be termln~l epoxy groups or lntern~l epoxy groups. The epoxides ~re of two generAl ~ypes: polyglycidyl com2ounds or psoducts derived from epoxldation of dienes or polyenes.
Polyglycldyl compounds contsin ~ plursllty of 1,2-epoxide groups derived ~rom the re~ctlon of a polyfunctional sctlve hydro~en contalnlng compound with ~n excess of en epihslohydrln under basic conditions. When the ~ctive hydro~en compound is polyhydric Alcohol or phenol, the resultlng epoxide resin cont~lns ~lycidyl ether groups.
Ex~mples o~ such poly(glycidyl ether) resins lnclude blsphenol A epoxy re~lns, epDxy novolsk resins derlved ~rom phenol-form~ldehyde And cresol-formaldehyde novolaks snd sim~l~r compounds.
Numerous examples sre ~vailable commercl~lly from Dow Chemlc~l Co. and Shell Chemic~l Co.
Other suiteble epoxy resins lnclude polyepoxides prep~red ~rom polyols ~uch ~s pent~erythritol~ glycerol, butanediol or trlmethylolprop~ne snd an eplhalohydrln.
''~ ' ' , ~7~
, Other polyfunction~l ~c~ive hydro~en compounds besides phenol~ Qnd ~lcohol~ m~y be used to prep~re the poly~lycidyl Qdductfi of thi~
lnvention. They lnclude ~mines, ~minoslcohols or ~minophenols, and polycarboxyllc arlds.
Examples of such ~dducts lnclude N,N-dlglycldyl snillne, N,N-dlglycidyl toluidine, N,N,N',N'-tetraglycidylxylylene di~mins, N,N,N',N'-tetraglycidyl-b~s(methylam~no) cyclohex~ne, N,N,N',N'-tetr~glycidyl-4,4'-dlsminodlphenyl methsne, ~nd the llXe.
Commerci~lly av~ ble resins of thls type lnclude Glyamlne*135 ~nd Glyflmine*125 (obtslned from F.I.C.
Corporstlon, S~n Fr~ncisco, CA.), Ar~ldlte MY-~20 (obt~ined from Clbs Geigy Gorporatlon) ~nd PGA-X ffnd PGA-C (obt~ined from The Sherwin~Willl~ms Co., Chlcago, Illinols).
Sult~ble polyglycldyl sdducts derived from amlno~lcohols lnclude O,N,N-trlglycldyl-4-sm~no-phenol, sv~llable 8s Araldlte*0500 or Araldlte*0510 (obt~lned from C~bs Geigy Corporatlon) ~nd O,N,N-triglycidyl-3-Qmlnophenol (av~l118bl~ 8s Gly~mine 115 from F.I.C. Corpor~tion).
Also suitsble for use herein ~re the glycidyl esters of car~oxylic BCidS. Such glycldyl esters include, for ex~mple, dlglycidyl phthalHte, dlglycldyl terephth~l~te, dlglycldyl isophth~l~te, and dlglycldyl adlp~te. There m~y also be u~ed polyepoxides such ~s trlglycldyl cyenurstes snd ~SOCyQnur~teS, and other epoxy-contslning m~terlals ~uch ~s copolymers of acryllc ~cld esters of 81Ycldol 6Uch as glycldyl scrylate and glycldyl * Trademark D-151~0 ' ~
.. :-- -.
methscrylate wlth one or more copolymerlzabl~e vinyl compound 9 .
The ~econd group of epoxy ~esins i8 prep~red by epoxld~tlon of dienee or polyenes.
Resins of thls typP include bis(2,3-epoxycyclo~
pentyl) ether, ~nd lts re~ctlon product~ wlth ethylene ~lycol which ~re de~cribed ln U.S. Pstent
However, ~ost epoxy formul~tions ~bsorb molsture whlch reduces their high temperQture properties. A~
~ result, they sre not suitable ~or use ~t 300DF or grester ~n ~ moisture ~turQted condition. There is therefore a need for ~esin systems which ~fford composites which csn retsln ~ high level of properties at 300F under such ~oisture ~turated conditions.
Most prepre~ resins designed for use at temperatures of 300F or higher ~re m~de by comblnlng bismaleimldes of Formul~ I with liquid coresct~nts containing other reactive groups such as ~mines, epoxldes, cysnstes or comonomers contslnlng -CH-CH2,~C=CH2, or -CH=CH- groups which can reac~ or polymerlze with the csrbon-cRrbon double bonds of the m~leimide groups.
N-~-O O
In the most common blsmsleimides, R is the resldue of ~n Rrom~tic diamine ~uch 8S methylene di~nlllne or rel~ted derlvatlves.
A wlde r~nge of blsmalelmlde comp~sltions based on dlfferlng ~romatic residues or blcnds of ~'7~
bismsleimides c~n be used, however. All of these bismaleimldes ~re sollds or glas~es at room temper~ture which requlre ll~uld coreact~nts ~n order to provide ~ processible ~nd useful resln ~or composite fAbricstlon.
The range o ~ultable llquid reactlve dlluents containing uns~turfited c~rbon-c~rbon double bonds, however, is ourrently very limited. M~ny of the ~v~ ble diluents ~re restricted by thetr lcw bolling points snd, therefore, hi~h volatility; by their odor; by their toxlclty ~ndtor problems with ~kin irrit~tion; by their poor ~bllity to dissolve bismelelmides; by their high viscosity which, s~in, limits the bismsleimlde solubllity ~nd ~lso le~ds to llttle or no tack in the formulation; by thelr poor th~rmsl st~billty or hydrolytic stabllity; by their lncompatibll1ty wlth othe~ formuls~lon modifiers; by their effect on the mechanlc,~l properties of the cured f~rmulation; ~nd/or by their tendency to c~use rapid cross-linking ~nd gellation of the bismaleimide formulation.
A need cle~rly exlsts, therefore, for new and effective reactlve dlluents which can overcome all or at lesst ~any of the ~bove noted problems.
SUMMARY OF THE_INVENTION
Applicsnt has discovered new blsmaleimide formul~tions contain1ng liquid reactive dlluen~s which Avoid substan~lally all of the cbove-noted dlssdv~nt~ges commonly sssoclste~ wlth the prior ~rt diluents.
More p~rtlcul~rly, ApplicQnt has discovered thst oleflnlc ethers and especi~lly allyl ethers c~n . ~
~" ~
~ct ~s dlluents for blsm~leimide for~ul~lon~ to provlde cured products wl th low water Qb~orption ~nd ~ wide range of glass trsnsltion temperatures ~Tg).
T8 velues of 350C and hi~her c~n be obtQined dependlng on the p~rtlcul~r ~ormul~tion.
An ~ddltion~l ~dv~nt~ge of the olefinlc ether/bism~lelmlde formulatlons ~ 8 their ~bility to B-~t~ge or ~dvance low v15~0sity formulat~ons to deslred vlscoslty sultsble, for example, for prepre~
tow or tspe f~brlc~tion. Unllke general ~ree-r~dlcal curlng resins, these formul~tions show a gradu~l lncre~se in viscoslty wlthout fiigns of gell~tion or ~n ebrupt exotherm. This fe~ture i~
useful ln optimizing a given formul~tion for u~e in specific composlte fsbricatlon technlques.
Moreover, unlike other dlluents such ~s divinylbenzene, oleflnlc ether reactive dlluents provlde 800d stablllty ln the uncured resin ~nd h~ve little or no odor. Addi~lonally, unllke m~ny low viscosity diluents such ~s st:yrene, the diluents of the present invention h~ve low volstllity ~t ~mbient temperatures.
In contrAst to other commonly ~v~llable sllyl dlluents such as disllyl phthal~te ~nd tri~llylisocysnur~te, the diluents o~ thls invention provide enhanced Tg v~lues ~nd/or mechanic~l propertles.
Still further, unlike diluen~s whlch cont~in resldu~l phenolic, hydroxyl, or other actlve hydro~en groups, the diluents of the present inventlon c~n be used ln con~unction wlth cy~n~te ester resins without premature gellatlon.
5 ..
.
So too, ln contr~st to diluents cont~inlng multlple ester bonds, ~he oleflnlc e~her dlluents of ~he present inventi~n provlde excellent ~her~al ~nd hydrolytic ~tability.
Fin~lly, unlike acryllc or methscryllc diluents, the diluents of the pre ent invention gener~lly do not ~ppear to cQuse skin sensitlvity or other toxlcity problems.
Speciflc~lly, the new resin formulations of the present invention comprise:
(l) bi~m~leimide; ~nd (li) st least one or more of 8 re~otlve diluent which may be descrlbed by the following general formulc:
II ~R3m EAr~ ZR3n where Z = O or S, snd where R ~ -CH'CH2, -CH2CH=CH2, -CH -C CH~, CH
-CH=CHCH3.
C~
- C ~ /
~2~ ~
r~ b~
~ C ~
--C~ C'~
~ z~
n > 1, m = 0 to 2, m ~ n ~ 2 Ar c ~ ~
~X~
in which X = ~lkylldene, Rryl, arylalkylldene, r S~ S02~ GO~
O O
- C - O -, - C - NH-, -O(CH2)nO-and where Ar msy option~lly be ~ubstltuted with ~lkyl, alkoxy, halogen, and other non-reactlve groups.
These formulstions msy optlonRlly cDnt~ln ~dditives such ~s thermopl~stlcs, epoxy reslns, am1ne hardeners, cyanete res~ns, filler6 or other modiflers ~nd may also contaln 8 ~tructus~l f~ber.
DETAILED DESCRIPTIO~ OF THE INVENTION
The allyl Qnd methallyl dtluents of thls lnvPntion are reQdlly prepared from ~v~ ble ~henol~c msterials ~nd ~llyllc h~lides. Numerous ~olvents including ~lcohols, ethers And dipol~r ~protic solvents such as dimethyl ~ormamlde, dlmethyl ~cet~mlde snd dlmethyl sulf~xide ~ay be , :' ' -:
~ ~ 7 L~ ~ L?~
used ~s ~ell ~s both hydroxlde ~nd csrbon~te b~es.
Propenyl ether~ msy be prep~red by b~se-c~talyzed lsomeri~tlon of the allyl ~thers. Methcds ~or the prep~r~tlon of ~lnyl ~thers ~re well known to ~hose ~kllled ln the art.
Preferred diluents inolude the followlng ~tructures:
~0 ~ o-cH2o~2 III
CH2=CH-CH ~
CH2=CHCH2-0 ~ l, ~ -CH2o~2 IV
lC:H2=CHCH~-O ~ CK ~2a ~ 2 V
CH2=CHCH2-o ~ o-CH2~o~2 VI
~-lS180 ~lX7~ 8 ,~ ~CH2CH~H2 V I I
CH2~H-CH2 CH2=CHcH2 ~cH2cH~H2 VI I I
~C H2CH5CH2 ~CH2~H=CH2 ~2-( H~2 X
2~ 2 ~12~1~2 CH2=CHCH2-O ~J o CH2CH=CH2 X I
o-CH2CH~CH2 .., . ~ .
., '~ .
7~ 8 CH2=cHC:H2~ ~cH2cH=cH2 XI I
,~ ~c H2~H~H2 X I 1 I
CH3 O-cH2CH=CH2 OCH
H2c H~H2 X I V
O-CH2CH~H2 ~2~2~(~2)~0-C~2CH--CH2 XV
n ~ 1-6 In all of the above structures, it ls posslble to substltu~e vlnyl ether, propenyl ether , .:
or meth~llyl ether groups for the ellyl ether ~roups æhow. Allyl ethers ~re ~he preferred oleflnlc ethers.
Additional ~terlQls whlch fsll under the bro~d ~cope of thi~ lnventlon ~re ~hose ol~flnlc ethers whlch ~re ~olld ~t ~bient temper~ture but whlch m~y be used ~s blends with other liqu~d diluen~s. Preferred ex~mples of these coreact~nts lnclude the diAllyl ether of biphenol, o bisphenol S, snd of naphth~lene diol 8S shown below:
CH2=CHCH2-o ~ o-cH2cH=cH2 XVI
O-CH2CH=CH2 5~ XV I I
0-CH 2CH=CH 2 C}12=CHCH2-0~ so24~ 0-CH2CH=CH2 XYI I I
74~L~ ~3 The bismalelmides ~ult~ble for use ln the formul~lons of this ~nvention ~re defined by structure I where R c~n be the resldue of an uromstlc or ~llphatic organlc comp~und. Preferr~d blsm~leimides include the following s~ructures wh~ch may be u~ed ~lone or 8S ~ixtures:
\,~C~3 ~ \ 3 CH~ Ic 3 ~ ~5~80 ~7~
~, ~0~ ' 3 CH3 C~ O
N~ N 3 o U o N~O~ 0~ N 3 o o o o ~ ~\`~S2 ~ ~C 3 o o o O O
,, o c ~ ~ ~ ~c 3 , ~ 3 .. . . .
~74~
o o ~ c~ C~ 3 o E~ c~ C 3 o , ~C~/ ~
~c~ 3 o o o o :'". ' :, .: ::,. :
~ ~ 7 ~
Il ~
C ~ C
O O
CH3 c ~C ~ ~
¢ lNC~2 1CCH2CHCH2CH N/ 3 CH~ ,RI~ C ~--CH,~ ~ 3 ~ where ~ ls the r~sldue of ~n ~romatlc dl~mine or ~mlnohydrazlde.) ''. ' - . :....
.'''", ~. .
1~74~3~
~ ther bismsleimides not speclfically shown Qbove may ~l~o be used in ~he present lnventi3n. It ~s ~lso po~slble to use bism~leimides ln ~hieh up to 50~ of ~he malelmlde groups have been repl~ced by ~ubstituted malelmide groups ~uch as methyl malemldes or hAlomale~mldes or by the n~dimlde, methyl nadimlde, or i~omaleimide groups ~hown below:
~/ 3 ~ T
~~ ,. a _x-~c~ c8~
where T = methyl, hslogen, hydro~en.
Portions of ~he mslemlde groups m~y ~lso be replaced by succintmide, phthsllmide, or ~ubstlt~ted succlnlmlde ~nd phthallmide ~roups.
An ~dvantag2 of cert~ln of the formulations of this inventlon ls thelr ~bility to be controllsbly "B-staged" or increas2d ln vlscoslty wlthout the common prob~em of Qell6tlon which ls assocl~ted w1th m~ny reactlve dlluents. In p~rtlcul~r, blends of the ~llyl ether of Eugenol (III) wlth Compimlde 353 (~ commerclslly ~v~ ble mixture of blsmaleimides obt~ined from Boots-Technochemle, Nottlngham, Engl~nd) pr~vide s very low viscosity resin (< 180 cps) at room temper~ture whlch is sultable for ln~ectlon into preformed msts of relnforclng flbers. ~dvsncement of thi~ resin ~t elev~ted temperatures ~uch OQ 120 - 150C can be c~rrled out to provlde a ~lmllsr resin of hl~her vi~coslty whlch ls ~uitHble for wet-wlndln~ or prepreg tow f~bric~tion. Gon~inued ~dvancement cRn be c~rrled out ~o prov~de ~ ~e~ln vi~coslty suitQble ~or film-eoating and prepreg tape febrle~tlon.
The low vlsco~ity of ~his and ~lmil~r resins c~n al~o be ad~u~ted by the addltion of thermop~stlc polymers, particulate fillers, ~nd other conventional resln sdditlves.
In addition to the blsmaleimides ~nd olefinic ether dlluents used in the formul~tions of the present lnvention, other reactive dlluent~ and modiflers m~y be lncluded ln the formulatlons.
Li~uid re~ctlve diluen~s which can be used as modifiers include N-vlnyl-2-pyrrolidin~ne, N-vlnyl csprol~ctsm, ethylene glycol dimeth~crylate, dlethylene glycol dimethacrylste, ethoxyl~ted bisphenol A dimethacryl~te, trlmethylolpropane tri~crylate, trimethylolpro1?ane trlmethacryl~te, pentserythri~ol triacrylate, pentaerythri~ol tetra~cryl~te, pent~erythrltol tetramethflcrylate, trl~llyl lsocy~nurate, trlAllyl cydnurste, di~llyl phthal~te ~nd its ifiomers, tetra~llyl pyromellltate, o,o'-dlallyl bisphenol A, Eugenol, trl~llyl trimellitste, divlnyl benzene, d~cyclopen~adienyl ecryls~e, dicyclopentadlenyloxyethyl acryl~te, v~nylcyclohexene monoepoxlde, 1,4-but~nediol divinyl ether, 1,4-dlhydroxy-2-butene, styrene, slpha methyl styrene, chlorostyrene, p-phenylstyrene, p-me~hylstyrene, t-butylstyrene, phenyl vlnyl ether, uns~tursted polyesters, vinyl ester resin~, ~nd ehe like. These comonomer~ ~re chQr~c~erized by the presence of one or more -CH~CH2,,G'CH2, or -C~CH- groups which c~n polymerlze or ~eact wlth the malelmlde groups of the bl~m~leimide.
Other llquld core~c~ants ~nclude epoxy resins whieh contain one or more epoxy ~roup~ havln~ -the following formul~:
o ~ ~ g_ The epoxy groups can be termln~l epoxy groups or lntern~l epoxy groups. The epoxides ~re of two generAl ~ypes: polyglycidyl com2ounds or psoducts derived from epoxldation of dienes or polyenes.
Polyglycldyl compounds contsin ~ plursllty of 1,2-epoxide groups derived ~rom the re~ctlon of a polyfunctional sctlve hydro~en contalnlng compound with ~n excess of en epihslohydrln under basic conditions. When the ~ctive hydro~en compound is polyhydric Alcohol or phenol, the resultlng epoxide resin cont~lns ~lycidyl ether groups.
Ex~mples o~ such poly(glycidyl ether) resins lnclude blsphenol A epoxy re~lns, epDxy novolsk resins derlved ~rom phenol-form~ldehyde And cresol-formaldehyde novolaks snd sim~l~r compounds.
Numerous examples sre ~vailable commercl~lly from Dow Chemlc~l Co. and Shell Chemic~l Co.
Other suiteble epoxy resins lnclude polyepoxides prep~red ~rom polyols ~uch ~s pent~erythritol~ glycerol, butanediol or trlmethylolprop~ne snd an eplhalohydrln.
''~ ' ' , ~7~
, Other polyfunction~l ~c~ive hydro~en compounds besides phenol~ Qnd ~lcohol~ m~y be used to prep~re the poly~lycidyl Qdductfi of thi~
lnvention. They lnclude ~mines, ~minoslcohols or ~minophenols, and polycarboxyllc arlds.
Examples of such ~dducts lnclude N,N-dlglycldyl snillne, N,N-dlglycidyl toluidine, N,N,N',N'-tetraglycidylxylylene di~mins, N,N,N',N'-tetraglycidyl-b~s(methylam~no) cyclohex~ne, N,N,N',N'-tetr~glycidyl-4,4'-dlsminodlphenyl methsne, ~nd the llXe.
Commerci~lly av~ ble resins of thls type lnclude Glyamlne*135 ~nd Glyflmine*125 (obtslned from F.I.C.
Corporstlon, S~n Fr~ncisco, CA.), Ar~ldlte MY-~20 (obt~ined from Clbs Geigy Gorporatlon) ~nd PGA-X ffnd PGA-C (obt~ined from The Sherwin~Willl~ms Co., Chlcago, Illinols).
Sult~ble polyglycldyl sdducts derived from amlno~lcohols lnclude O,N,N-trlglycldyl-4-sm~no-phenol, sv~llable 8s Araldlte*0500 or Araldlte*0510 (obt~lned from C~bs Geigy Corporatlon) ~nd O,N,N-triglycidyl-3-Qmlnophenol (av~l118bl~ 8s Gly~mine 115 from F.I.C. Corpor~tion).
Also suitsble for use herein ~re the glycidyl esters of car~oxylic BCidS. Such glycldyl esters include, for ex~mple, dlglycidyl phthalHte, dlglycldyl terephth~l~te, dlglycldyl isophth~l~te, and dlglycldyl adlp~te. There m~y also be u~ed polyepoxides such ~s trlglycldyl cyenurstes snd ~SOCyQnur~teS, and other epoxy-contslning m~terlals ~uch ~s copolymers of acryllc ~cld esters of 81Ycldol 6Uch as glycldyl scrylate and glycldyl * Trademark D-151~0 ' ~
.. :-- -.
methscrylate wlth one or more copolymerlzabl~e vinyl compound 9 .
The ~econd group of epoxy ~esins i8 prep~red by epoxld~tlon of dienee or polyenes.
Resins of thls typP include bis(2,3-epoxycyclo~
pentyl) ether, ~nd lts re~ctlon product~ wlth ethylene ~lycol which ~re de~cribed ln U.S. Pstent
3,398,102. Commercl~l exsmples of the~ epox1des lnclude vlnylcyclohzxene dioxlde, ~.~., "ERL-4206"
(obtsined from Unlon CQrblde Corp.), 3,4-Qpoxycyclo-hexylmethyl 3,4-epoxycyclohexane c~rboxylate, e.~., "ERL-4221" ~obt~ined from Union Csrbide Corp.), 3,4-epoxy-6-methylcyclohexylmethyl 3,4~epoxy-6-methylcyclohexsne carboxyl~te, e.~., "ERL-4201"
(obt~lned from Union Csrblde Corp.), bis(3,4-epoxy-6-methylcyclohexylmethyl) ~dlp~te, e.g., "ERL^4289" (obtslned from Unlon Csrbide Corp.), dipentene dioxlde, e.g., "ERL-4269"
(obtalned from Union Csrbide Corp.), 2-(3,4-epoxycyclohexyl-5,5-spLro-3,4-epoxy)cyclo-hexanemet~dioxane, P.g., "ERL-4234" tobtained from Union Carbide Corp.) ~nd epoxldized poly-but~dlene, e.g., "Oxlron* 2001" (obtalned from FMC Corp.) Other epoxy resins not speciflcally described above msy ~lso be used ~s modiflers ln the bismaleimide Formul~tions of ~he present invention.
Also included as epoxy ~odlflers are epoxy-terminated thermopl~stic polymers ~uch ~s epoxy-termin~ted polysulfone ~nd other slmil~r resins.
If epoxy reslns are used, lt 1~ deslrsble to sdd ~n ~rom~tic di~mine to the formuletion. The * Trademark 3 L~
dl~mlne should have ~ low level of re~ctivity ~lth epoxy resin ~nd the bism~lelmide ~t room tempers~ure. Sult~ble dlamlnes lnclude
(obtsined from Unlon CQrblde Corp.), 3,4-Qpoxycyclo-hexylmethyl 3,4-epoxycyclohexane c~rboxylate, e.~., "ERL-4221" ~obt~ined from Union Csrbide Corp.), 3,4-epoxy-6-methylcyclohexylmethyl 3,4~epoxy-6-methylcyclohexsne carboxyl~te, e.~., "ERL-4201"
(obt~lned from Union Csrblde Corp.), bis(3,4-epoxy-6-methylcyclohexylmethyl) ~dlp~te, e.g., "ERL^4289" (obtslned from Unlon Csrbide Corp.), dipentene dioxlde, e.g., "ERL-4269"
(obtalned from Union Csrbide Corp.), 2-(3,4-epoxycyclohexyl-5,5-spLro-3,4-epoxy)cyclo-hexanemet~dioxane, P.g., "ERL-4234" tobtained from Union Carbide Corp.) ~nd epoxldized poly-but~dlene, e.g., "Oxlron* 2001" (obtalned from FMC Corp.) Other epoxy resins not speciflcally described above msy ~lso be used ~s modiflers ln the bismaleimide Formul~tions of ~he present invention.
Also included as epoxy ~odlflers are epoxy-terminated thermopl~stic polymers ~uch ~s epoxy-termin~ted polysulfone ~nd other slmil~r resins.
If epoxy reslns are used, lt 1~ deslrsble to sdd ~n ~rom~tic di~mine to the formuletion. The * Trademark 3 L~
dl~mlne should have ~ low level of re~ctivity ~lth epoxy resin ~nd the bism~lelmide ~t room tempers~ure. Sult~ble dlamlnes lnclude
4,4'-diaminodlphenyl ~ulfone, 3,3'-di~m~nodlphenyl sulfone, 3,4'-dlamlnobenzophenone, 4,4'-dl~mlno-benzophenone, 4,4'-bi 8 ( 3-aminophenoxy) diphenyl sulfone, and the llke.
A ~tolchlometry of 0.1 to 1.0 equivalents of -NH per equlv~lent of ~1,2 epoxide group plus m~leimlde group) msy be used.
Diamlnes may ~lso be used even if no epoxy ls used. In this case the dlamlnes m~y re~ct prior to or during the cure cycle with the bism~leimldes.
When epoxies ~re present, the dl~mlnes may react wlth either the epoxy or m~lelmide g~oups.
The composltion m~y ~ddltionally conts1n ~n flccelerator to lncresse the rate of cure of the epoxy plus amlne re~ction. These ~ddltives m~y also be used to incre~se the de~ree of cure of ~n epoxy resin in the ~bsence of ~n smlne hsrdener.
Accelerators whlch may be used herein include Lewis Aclds; amlne complexes, ~uch as ~F3~monoethylamine, BF3-piperdlne, 8F3-2-meehylimidazolei ~mines, such ~s lmld~zole and its der1vatlves, ~uch ~s 4-ethyl-2-methyllmldazole, l-methylimld~zole, 2-methyllmidszole; N,N-~lmethylbenzyl~mine; Qcld ~lts of tertl~ry amlnes, such es the p-toluene ~ulfonlc acld:lmidszole complex, sQlts of trifluoro meth~ne sulfonlc ~cld, such ~s F~-520 tob~ined from 3M Compsny), or~nopho~phonlum h~lldes ~nd dicy~ndl~mide. If u~ed, ~he sccelerator m~y ~e from 1 to 6 percent by welght of the epoxy component.
~-lslao ~7~
The composition ~y al80 cont~ln compounds wlth one or more cyanate ester ~roups.
By cysnate ester 1B me~nt ~ compound hAving Bt le~st one cy~nate group ln its molecule. The cy~n~te ester is represented by the formul~
R - (O-C3`~) whereln R is ~ residue derived from ~n ~romstic hydrocsrbon selected from the QrOUp consistlng of benzene, biphenyl ~nd nsphthalene, or 8 residue derived from a compound ln which at least ~wo ben~ene rlngs are bonded to each other by ~ brid~ing member selected from the group consistlng of ~2 wherein Rl and R2 Qre the sam~e or dlfferene Rnd e~ch r~presents a hydrogen ~tom or an ~lkyl group cont~lnlng 1 to 4 c~rbon ~toms, Il -o-, -CH20CH2-, -S-, -c-, -o-c-o-, -S-, -s-, o o o o l -o-P-o and -O-P-O-;
Il 11 O o ~ald srom~tic nucleus i5 optlonally substituted by B
~ubstltuent ~elected from the group consi6tlng ~f Hlkyl ~roups containln~ 1 to 4 c~rbon ~toms, ~lkoxy ~roups cont~lnln~ 1 to 4 carbon atoms, chlorlne and D-lslao ~7'~ 3 bromlne; m 1~ an inte~er of 1 to 5, and th~ cyanate group ls alway~ dlrPctly bonded to the ~rom~tlc nucleus.
Ex~mples of the cyanate ester lnclude cy~n~tobenzene, dicy~natobenzene;
1,3,5-tr~cy~n~tobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dlcy~nston~phthAlene;
1,3,6-tricy~naton~phth~lene; 4,4'-dicy~nAtobiphenyl;
bls(4-cyanstophenyl)methane;
2,2-bis(4-cy~n~tophenyl)propane, 2,2-bis(3,5-dimethyl-4-cy~n2tophenyl)prop~ne, 2,2~bis(3,5-dichloro-.4-cy~natophenyl)propQne, 2,2-bls(3,5-dlbromo-4-dlcy natophenyl)prop~ne;
bis(4-cy~n~tophenyl)ether;
bis(4-cysnatophPnyl)thloether;
bis(4-cyanatoph~nyl)sulfone;
tris(4-cysn~tophenyl)phosphlte;
tris(4-cysnatophenyl)phosph~te;
bls(3-chloro-4-cyanstophenyl)methane; cyan~ted novol~k; cy~nsted blsphenol termin~ted polycarbon~te or other thermoplhstlc oligomer; ~nd mixtures thereof.
The ~bove mentlonefl cy~n~te esters ~ay be used ~s mixtures.
Prepolymers m~y be used contalning ~
symme~ricQl trlazine rln~ which ls prepared by the trimeriz~tion of the cy~nate groups of ~he Cy~nQte ester, ~nd whlch have an ~versge molecular wel~ht of ~t le~st 400 but no more thdn 6,000. Such prepolymers can be prepared by thermally polymerizlng the ~bove cy~nste esters ln the presencs or absence o~ ~ cst~lyst.
'3 - 23 ~
The cy~n~te e~ter can be used ~n the form of ~ mixture of the monomer ~nd th~ prepolymer.
Commerei~lly ~val~a~le ~cterials cont~ining cy~nate ~ster~ may be obtQined from Mi~subi~hl GRS
Chemical Co., Tokyo, Jsp~n ~nd Cel~ne~e Specl~l~y Resins Company, J~fferson, KY.
The ~ompositlons of thi~ inYention ~ay optlonally contfiin a thermopl~tlc polymer. These m~teri~ls have beneflcial effects on the viscosity ~nd film strength characterl~tlc~ of the bismaleimlde/liquld coreactAnt mixture ~nd m~y ~lso h~ve beneflclal effects on the properties of reinforced composites mAde ~rom these resins.
The thermoplRstlc polymers u~ed ln this inventlon include polyarylethers of formul~ XIX
which ~re described in U.S. P~tents 4,108,837 ~nd 4,175,175, -~0 - R' - O - Rll~n XIX
wherein R' is ~ residuum of El dihydrlc phenol such ~s blsphenol A, hydroquinone, resorclnol, 4,4-blphenol, 4,4'-dlhydroxydiphenyl su~fone, 4,4'-dihydroxy-3,~' 5,5'-tetr~methyldiphenyl sulfide, 4,4'-dihydroxy-3,3',5,5'-tetr~methyl-dlphenyl sulfone ~nd the llke. R" 1~ a residuum of a benzenoid compound susceptlble to nucleophlllc sromatlc ~ubstleution reac~lons such ~s 4,4'-dichlorodlphenyl sulfone, 4,4'-dlflurobenzo-phenone, ~nd the like. The ~verage v~lue of n 18 from ~b~ut 8 to about 120.
~7~8 Other suitable poly,~rylethers Qre de~crlbed in U.S. P~tent 3,332,209.
Also 3ult~ble ~re p~lyhydroxyether~ of the formuls:
t - R - o - cH2 - cH - CH2tn OH
XX
where R hss the s~me me~ning ~s ~or Formuls XYIII
~nd the ~vera~e v~lue of n 1~ between Hbout 8 snd about 300. Other ~ult~ble thermoplastlcs include poly (c-csprola tone); polybut~dlene;
polybutadlene/~crylonltrlle copolymers, lncludlng those option~lly cont~ining epoxy, vlnyl, ~crylic, methacrylic, amlnei carboxyl, hydroxy, or thlol groups; polyesters, such as poly(butylene terephthalete) and poly(ethylene terephth~late);
polyetherimides ~uch BS the Ultem*resins (obtalned from the General Electric Compcny); polycarbon~te su~h ~s the Lex~n reslns (obtalned from the Genersl Electric Company); scrylonitrile/butadlene/s~yrene copolymers; polyamldes fiuch as nylon 6, nylon 6,6, nylon 6,12, and Trog~mid T (obt~ined from Dynamit Nobel Corpor~tion); poly(~mldelmides) such BS Torlon*
(obtained from Amoco Chemicel Corpo~tion, Naplervllle, ~L); polyolefln~; polyethylene oxlde;
poly(butyl meth~cryl~te); imp~ct-modlfled polystyrene; sulfon~ted polyethylene; poly~ryletes * Tr~demark 6~
~ 8 such ss tho~e derived from blsphenol ~ ~nd l~ophthslic ~nd terephth~llc scld; poly(2,6-dlmethyl phenylene oxide) ~nd lts copolymers; polyvlnyl chlorlde ~nd lt8 copolymer~; poly~cee~
polyphenylene sulflde ~nd the llke.
Poly(vinyl ~cetate) snd copolymers of vinyl acetdte wlth other vinyl ~nd acryllc monomers m~y slso be used. Thermoplastics auch es 13~ profile ~ddltives, for ex~mple, W -40A, m~y ~1BO b~ u8ed.
Also sultabl~ sre vinyl methyl or vlnyl phenyl silicone rubbers such as polymers of the ~ormula -R2S10- whereln up to lOS of the R ~roups ~re ~inyl, the remslnder being either methyl ~nd/or phenyl.
Psrticularly 8U ltable ~re rubber modifiers, such ss but~dlene polymers and but~diene/~crylonitrile copolymers lncluding those option~lly cont~lning termln~l ~nd/or pendent smlne, epoxy, csrboxyl, hydroxyl, thlol, or uns~t~r~ted double bond groups, ~uch as ~crylstes or methscrylstes or vinyls. The~e Rre exempllfied by the Hyc~r Re~c~lve Liquld Polymers ~Ysll~ble from B.F. Goodrich, the 1,2-polybut~dlene resins ~v~ ble from Nippon Soda Co., the polybutsdiene reslns ~vallsble ~rom Arco Chemic~l Co. (~s poly-BD
reslns) and others. Elastome~s such as e~hylene/Acrylic copolymers, exempllfied by the V~m~c*reslns av~ ble from DuPont, end other el~stomerlc polymers ~nd copolymer m~y ~l~o be used. Also suit~ble are the polyester elastomers ~uch as the Vitel*resins tVitel* 307, etc.) vhlch are dvailsble from B.F. Goodrich.
* Trademark r ~ ~
~4V'~
` 26 -~ he preferred thermopl~stics include polysulfones, phenoxy res~ns, polysrylates, the butadlene/~crylonltrile copolymers descr1be~ above and the polyester el2stomer~. Mlxtures of such thermoplsstlc modlfiers m~y Qlso be u~ed.
The ~tructursl flbers which ~re u~Eul ~n thls invention include c~rbon, gr~phi~e, gla~s, ~llicon carbide, poly(benzothl~zole), poly(benzimldszole), polytbenzoxazole), ~lumlnum, tltanlum, boron, ~nd ~rom~tic polysm~de fibers.
These flbers ~re chQracterlzed by a tenslle stren~th f Bre~ter thsn 100,000 psl, ~ tenslle modulus of 8~eater th~n two mill1On psi, ~nd 8 decompositlon temper~ture of 8reater than 200C. The flbers may be used in the form of contlnuous tows (lO00 to 400,000 Eilaments each), woven cloth, whlsXers, choppecl fiber or random mQt. The preferred ~lber~
~re c~rbon flbers, aroms~lc polysmlde fibers, such ~s Kevlar*49 flber (obtained from E.I. DuPont de Nemours, Inc., Wllmlngton, DE), and slllcon c~rblde fibers.
The composltlons of the resin formulstions of ~he lnventlon contsin 1 to 99 wel~ht percent, prefersbly 20-90 percent of the blsmaleimlde; 1 to ~bout 70 perc~nt, preFer~bly 10 to 60 percent of the olefln ether coreactant; 0 - 50 percent of an Qddltlon~l mlxture of cDreact~nts comprlsing molecules wlth one or more smino, epoxy, ~yan~te, vlnyl groups such as -CH=CH~,~C~CH2, or -CH-CH-snd other functlon~litles ~s described ~bove; snd 1 to ~bout 40 percent, preferably 2 to 30 pe~cent of other ~dditlves, 8uch ~s thermoplas~ic poly~ers and other core~ctants.
* Trademark ~ I
- : .
~ J~
AddltionQl component~ ln the compo~itlon lnclude lnltiator~ for vlnyl polymeriz~tion ~uoh ~s di-t-~utyl peroxlde, dicumyl peroxlde, 1,1-~18 ( e -bu~ylperoxy) cyclohexane, 8Z o bls-(isobutyro-nitrile~, t-butyl perbenzoate, ~nd the like. The inlti~tor comprlses from 0 to 3 percent by we~gh~ of ~he total composl~lon.
Inhlbitors for vlnyl polymerl~tlon~ may also be used. They include hydroquinone, ~-butyl hydroquinone, benzoquinone, p-me~hoxyphenol, ~d 4-nltro-m-cresol. Inhlbitors sre present ln ~mounts of from 0 to 2 percent by wei~ht of the total composition.
When 3 structur~l flber is u~ed, the ~mount of flber ln the total compo~ltlon ls between sbout 10 and ,~bout 90 percent by wei~h~, prefer~bly between about 20 to about 85 percent by wei~ht.
Preimpregnated relnforoement may be made from the composltions of this invention by ~ombining the resin formulations wlth a structural fiber.
Preimpregneted relnforcement msy be prepsred by ~everal technlques known ln the art such as wet wlnding or hot melt. In cne ~ethod of makin8 ~mpregnA~ed tow or undirection~l tape, the resln is first coated ~s 8 thin fllm on release pAper. TWo rolls of thls co~ted psper plus sligned tows of carbon flber ~re then pressed together ond p~3sed through a serles of hested rollers to effect wet-out o~ the Elber tows by the resln. The thusly formed prepreg ls then ~llowed to cool ~nd taken up on ~pool.
Compssites may be prep~red by curln~ the prelmpregn~ted reinforcement usln heat ~nd optlonally pressure. V~cuum b~g/Autoclave cures ~ork well wlth these composltions. L~mlnates m3y also be prepared vi~ wet l~y up followed by compression moldln~, resin transfer ~oldlng, or by res~n in~ection, as descrlbed ln Europe~n PA~ent Application 0019149 published November 26, 19aO.
Typic~l cure temperetures are lOO~F to 600F, prefer~bly 1~0F to 490F.
The compositlons of this invention ~ay also be used for fll~ment wind1ng. In thls composite f~bric~tlon process, contlnuous reinforcement in the form of t~pe or tow - either prev~ously ~mpregnAted w~th resin or impregnsted during winding - i~ plsced over a rotQting snd removable form or mandrel in 8 previously determined psttern. Generally ~he sh~pe iS Q surface of revolutlon ~nd cont~lns end closures. When the proper number of l~yers are applied, the wound form ls cured ln sn oven or ~utocl~ve and the mandrel re~oved.
Tscky drsp~ble prepreg c~n be obtained with a wide v~rlety of composltlons. Long prepre~ ~helf llves cQn be obtAlned-typica,Lly one to four weeXs.
The compositions of th~s lnventlon may be used ~s matrlx reslns for composites, hlgh temperature coatlngs, and ~dhesives. ~en relnforced wlth structural fibers, ~hey m~y be used ~s Aircr~t p~rts ~uch as wlng ~klns, wing-to-body falrings, floor psnels, flaps, radomes; 8S
au~omotive parts, ~uch ~s drlve sh~fts, bumpers, snd springs; ~nd QS pressure vessels, tanks snd pipes.
~-~5180 .,, They are ~lso ~ultQble for protectlve ~rmor on mllitary vehlcles ~nd aporting goods applic~tlons such 8s golf ~hsfts, tenni r~cket~, ~nd fl~hln~
rods.
In addltlon to ~tructural flber~, ehe composition mYy ~180 cont~in partlculate fillers such ss talc, micQ, c~lcium carbon~t~, aluminum trlhydrate, glass microb~lloons, phenolic thermospheres, and c~rbon bl~cX. Up to half of the weight structur~l flber in the compositlon ~y be repl~ced by flller. Thlxotropic a~ents ~uch 9S
fumed sllic~ may elso be used.
EXAMPLES
The following e~amples servP to ~l~e ~peçl$1c illustrations of the pr~ctice of th1s inventlon but they are not intended in ~ny way to limlt the ~cope of thls inventlon.
ExsmPle l. PrepsrRtlon of 2-methoxy 4-allyl-1-allyloxybenzene (ally~ ether of ugenol).
A 5 Q 4-neck flssk equlpped with sn overhead stlrrer, addltion funnel, reflux condenser, nltrogen inlet ~nd outlet, arld he~tlng mantle w~s ch~rged with 2 Q n-prop~nol, 656.8 ~ of Eu8enol, ~nd 165.0 8 of freshly opened 30d~u~ hydroxlde pellets. The mixture w~s s~lrred and heated at reflux until the sodlum hydroxlde h~d dlssolved.
400 ml of allyl chlorlde was then slowly added over 20 mlnutes while ~entle reflux was contlnued. The lemon yellow reactlon mlxture ~as then reFluxed An ~ddltlonsl 5 hour~ Qnd st~rred ~t room temperQture overnlght.
~-15180 The preclpit~ted ~odlum chlorlde was removed by filtr~tion and the n-propanol ~s ~tripped under vacuum on ~ rotsry ev~por~tor. The crude product w~s d~luted with 2 Q of ~ethylene chloride ~nd th~t 601ution wsshed twice with w~ter and ~wice wlth brine. The methylene chloride w~s removed under vQcuum on a rot~ry ev~por~tor ~nd the product then filtered through sodlum sulph~te ~nd held undzr v~cuum overnlght. The yleld of liquld dlluent w~s 811 ~ snd the NMR w~s consistent with the expected structure shown below.
~0 CH2C~I=CE12 CH2=CH-CH ~
The bolling polnt of this diluent ~as over 250C t ~tmospheric pressure. The diluent w~s st~ble up to th~t temperQture ~nd, even when cured in the presence of a free r~ldical lnhibitor (see schedule A ~s discussed herl31nbelow), showed only partl~l cure ~nd could not be tested mechanlc~lly.
Ex~mPle_2. Prepar~tion of 4,4~-dl~llyloxydlphenyl-isopropyli.dene (diallyl ether o~ ~isphenol A).
A 3 ~ 4-neck flask equlpped ~s in Ex~mple l was ch~r~ed wlth 1 Q n-prop~nol, 22B ~
of Bisphenol A, ~nd B2.5 g of freshly opened sodium hydroxlde pellets. The mlxture WBS stirred and he~ted ~t reflux untll the ~odlum hydroxide h~d dlssolved ~nd 200 ml ~f Qllyl chlor~de was then added ~lowly whlle gentle re~lux w~s continued. The ........ , . ,. ., -re~ctlon m~xture w~s refluxed an ~ddltlonsl 6 hours and then stlrred ~t ro~m tempersture oYernl~ht.
The preclpit~ted sodlum chloride ~as removed by filtratlon ~nd the n-propanol w~s str~pped under v~cuum on ~ rotsry ev~porQtor. The crude product w~s dlluted with 1 ~ of methylene chlorlde ~nd thst solution w~shed ~wlce with w~ter And once wlth brine. The methylene chlorlde was strlpped OR ~ rot~ry ev~porRtor ~nd the product flltered through sodlum ~ulphate ~nd held under vacuum overnlght. The yleld was 148 8 ~nd the NMR
W8S conslstent with the expected structure shown belo~.
c~2=CHCH2{)4~C~o_CH2CH~12 The bolling point of this dlluent was over 250C ~t atmospherlc pressure. The dlluent W8S
stsble up to th~t temperature ~nd, even when cured in the presence of ~ free radic~l inltlator (cure schedule A ~s discussed hereinbelow), showed only p~rtl~l cure ~nd could not be tested mechsnlc~lly.
Example 3. Prepara~ion of me~a-dlallyloxybenzene.
A 3 Q 4-neck fl~sk equlpped as ln Exsmple 1 W85 char~ed wlth 1.5 Q
dlmeehylform~mide, 110.1 8 re&orcinol, ~nd 345 ~ of ~nhydrous potasslum c~rbon~te. The mlxeure ~8S
~tirred and hested ~t 100C untll most of the csrbonate w~s in ~oluti~n and 20Q ml of ellyl ~-151~0 - ..
.. .
~'~ 7 ~
- 3~ -chlorlde w~s then ~dded over about 1 hour. Heatlng w~s continued for 5.5 more hour~ snd the ~ct~on ~s then ~tlrred overnl~ht at ro~m temperature.
The resction mlxture w~s dlluted wlth 1 ~
of methylene rhlorlde snd th~t solutlon W8S washed ~ix tlmes with brlne. The methylene chlorlde ~olution w~s ~hen flltered thrDugh sodlum ~ulphate and the methylene chlorlde was removed under vacuum on a rot~ry ev~por~tor. The llquld residue WBS held under vacuum overnlght. The yield w~s 157 ~ ~nd ~he NMR w~s consi~ent with ~he expected fitructure ahown bels~ .
CH2~cH2~ 0~2CH¢H2 The boillng polnt of this diluent was over 250C ~t stmosphPric pressure. The diluent w~s stable up to thst temper~ture and, sven when cured ln the presence of a free r~dical inl~i~tos (cure schedule A BS d1scussed hereinbelow), ~howed only p~rtial cure and could not ~e tested mechanlc~lly.
Ex~mPle 4. Prep~ration of 1,3-dlallyloxy-2-methyl-benzene.
A 3 Q 4-neck fl~sk equlpped 8S ln Example 1 W8S ch~rged with ~.5 Q of dimethyl ~cet~mide, 124 g of 2-me~hylresorcinol, and 345 g of ~nhydrous pot~ssium carbonRte~ The mixeure was stlrred and heated to lOODC. A 200 ml`chsr~e of ~llyl chlorlde WHS then ~dded over 1 hr. ~eatin8 and ~tirrin~ were con~lnued for 5.5 hrs. The mlxtur~ ~s ehen ~tirræd snd let cool overni~he.
, : . ~ , .
, ~ 7 The resctlon mlxture WBS dlluted wlth 2 ~
of methylene ehloride and th~t ~olutlon ~as ~hed with four 2 ~ portlons of water, twice wlth dllute ~.25M) pot~sslum csrbonste, ~nd four 2 ~ portion~
of brine to glve a light ~old solution. The 801utlon was flltered through ~odlum 6ulf~te snd the methylene hlorlde was then removed on a rot~ry evaporator to glve 191 ~ of ~ liquld product. The NMR was consistent wlth the expected structure ~hown belo~.
~2~2~-~2~2 The boillng point of this diluent w~s over 250G.
The diluents prepsred ln Ex. 1-4 were ~11 odor-free or possessed A mlld odor. All had bo11ing poin~s of over 250C and were ~table, showing no signs of gellHtlon up to thst temperature, even ln the 8bsence of lnhlbltors.
ExsmPle 5. Bismslelmlde/dlluent mixture.
A mlxture of 6.6 g of SED-M bl~meleimide (4,4'-bls(3-m~leimldophenoxy) dlphenyl sulfone) Qnd 3 4 8 of the dlsllyl ether of Bi~phenol A (product in Example 2) was blended on a rot~ry ev~p~rstor ~t 125C untll homogeneous. It was mixed and hel~
under vacuum sn ~ddlt1onsl 10 mlnutes for de-g~sslng ~nd then poured into ~ small casting frfime formed from glsss pl~tes and B l/16" Teflon sp~cer gesXet.
* Trademark 7 ~
The clear mixture WAS cu~ed ~ccor~lng t~ ~he followln~ schedule:
25~C~ 79C ~t- 1.5~/min. Hold 2 hr~.
7~C~ 177C ~t 1.5/mln. Hold 4 hr~.
177C~ 246C ~t l~/min. Hold 4 hrs.
246~C ~ 25C at 1.5/min.
The cured c~sting was found to h~ve ~ Tg (pe~k of damping curve) of 240C (DMA sc~n st 5C/min.~ and absorbed 1.6S wster dur~ng ~ 2-week soak at 160F.
ExsmPles 6-20.
The procedure of Exsmple 5 w~s repeated using the ~ngredients llsted ~n T~ble I. The T~ nnd wR~er absorption d~t~ for the cured m~terials is slso listed in T~ble I~
In some cases, an ~ltern~te cure schedule w~s used, Qnd det~lls of the cure schedules ~re given in the T~ble notes. Some resins were mixed at 140C lnste~d of 125~C.
D~lSlflO
'7~
TABLE I
Formul~tlon C~stings (Bi~mslelm1de/D~luent) E~ Bis~ lmldaDllu~nt Cur~ ~ ~31120 Abl;orbi~d -6.6 SED~ll 3.d D~aA~ A 245 2.1 6 7.~ SEDMI 2.6 EC07 A ~ 2.6 7 7.6 SEOMI 2.4 DERq ~ 2B5 2.1 8 6.5 B~P2 ~.5 DBA ~ 225 ~.5 9 6.5 B~2 i.5 DEBA B 222 ~. l 7.4 BA~P2 2.6 DEBA B 2~0 2.6 Il 7.1 ~pp2 2.6 EC0 A ~IC 2.6 12 7.d B~PP 2.6 DAMR9 A 270 13 7.0 BA~ ~.0 EC0 A 265 Z.l 14 6.9~4 ~.l EC0 ~ ~20 5.
A ~tolchlometry of 0.1 to 1.0 equivalents of -NH per equlv~lent of ~1,2 epoxide group plus m~leimlde group) msy be used.
Diamlnes may ~lso be used even if no epoxy ls used. In this case the dlamlnes m~y re~ct prior to or during the cure cycle with the bism~leimldes.
When epoxies ~re present, the dl~mlnes may react wlth either the epoxy or m~lelmide g~oups.
The composltion m~y ~ddltionally conts1n ~n flccelerator to lncresse the rate of cure of the epoxy plus amlne re~ction. These ~ddltives m~y also be used to incre~se the de~ree of cure of ~n epoxy resin in the ~bsence of ~n smlne hsrdener.
Accelerators whlch may be used herein include Lewis Aclds; amlne complexes, ~uch as ~F3~monoethylamine, BF3-piperdlne, 8F3-2-meehylimidazolei ~mines, such ~s lmld~zole and its der1vatlves, ~uch ~s 4-ethyl-2-methyllmldazole, l-methylimld~zole, 2-methyllmidszole; N,N-~lmethylbenzyl~mine; Qcld ~lts of tertl~ry amlnes, such es the p-toluene ~ulfonlc acld:lmidszole complex, sQlts of trifluoro meth~ne sulfonlc ~cld, such ~s F~-520 tob~ined from 3M Compsny), or~nopho~phonlum h~lldes ~nd dicy~ndl~mide. If u~ed, ~he sccelerator m~y ~e from 1 to 6 percent by welght of the epoxy component.
~-lslao ~7~
The composition ~y al80 cont~ln compounds wlth one or more cyanate ester ~roups.
By cysnate ester 1B me~nt ~ compound hAving Bt le~st one cy~nate group ln its molecule. The cy~n~te ester is represented by the formul~
R - (O-C3`~) whereln R is ~ residue derived from ~n ~romstic hydrocsrbon selected from the QrOUp consistlng of benzene, biphenyl ~nd nsphthalene, or 8 residue derived from a compound ln which at least ~wo ben~ene rlngs are bonded to each other by ~ brid~ing member selected from the group consistlng of ~2 wherein Rl and R2 Qre the sam~e or dlfferene Rnd e~ch r~presents a hydrogen ~tom or an ~lkyl group cont~lnlng 1 to 4 c~rbon ~toms, Il -o-, -CH20CH2-, -S-, -c-, -o-c-o-, -S-, -s-, o o o o l -o-P-o and -O-P-O-;
Il 11 O o ~ald srom~tic nucleus i5 optlonally substituted by B
~ubstltuent ~elected from the group consi6tlng ~f Hlkyl ~roups containln~ 1 to 4 c~rbon ~toms, ~lkoxy ~roups cont~lnln~ 1 to 4 carbon atoms, chlorlne and D-lslao ~7'~ 3 bromlne; m 1~ an inte~er of 1 to 5, and th~ cyanate group ls alway~ dlrPctly bonded to the ~rom~tlc nucleus.
Ex~mples of the cyanate ester lnclude cy~n~tobenzene, dicy~natobenzene;
1,3,5-tr~cy~n~tobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dlcy~nston~phthAlene;
1,3,6-tricy~naton~phth~lene; 4,4'-dicy~nAtobiphenyl;
bls(4-cyanstophenyl)methane;
2,2-bis(4-cy~n~tophenyl)propane, 2,2-bis(3,5-dimethyl-4-cy~n2tophenyl)prop~ne, 2,2~bis(3,5-dichloro-.4-cy~natophenyl)propQne, 2,2-bls(3,5-dlbromo-4-dlcy natophenyl)prop~ne;
bis(4-cy~n~tophenyl)ether;
bis(4-cysnatophPnyl)thloether;
bis(4-cyanatoph~nyl)sulfone;
tris(4-cysn~tophenyl)phosphlte;
tris(4-cysnatophenyl)phosph~te;
bls(3-chloro-4-cyanstophenyl)methane; cyan~ted novol~k; cy~nsted blsphenol termin~ted polycarbon~te or other thermoplhstlc oligomer; ~nd mixtures thereof.
The ~bove mentlonefl cy~n~te esters ~ay be used ~s mixtures.
Prepolymers m~y be used contalning ~
symme~ricQl trlazine rln~ which ls prepared by the trimeriz~tion of the cy~nate groups of ~he Cy~nQte ester, ~nd whlch have an ~versge molecular wel~ht of ~t le~st 400 but no more thdn 6,000. Such prepolymers can be prepared by thermally polymerizlng the ~bove cy~nste esters ln the presencs or absence o~ ~ cst~lyst.
'3 - 23 ~
The cy~n~te e~ter can be used ~n the form of ~ mixture of the monomer ~nd th~ prepolymer.
Commerei~lly ~val~a~le ~cterials cont~ining cy~nate ~ster~ may be obtQined from Mi~subi~hl GRS
Chemical Co., Tokyo, Jsp~n ~nd Cel~ne~e Specl~l~y Resins Company, J~fferson, KY.
The ~ompositlons of thi~ inYention ~ay optlonally contfiin a thermopl~tlc polymer. These m~teri~ls have beneflcial effects on the viscosity ~nd film strength characterl~tlc~ of the bismaleimlde/liquld coreactAnt mixture ~nd m~y ~lso h~ve beneflclal effects on the properties of reinforced composites mAde ~rom these resins.
The thermoplRstlc polymers u~ed ln this inventlon include polyarylethers of formul~ XIX
which ~re described in U.S. P~tents 4,108,837 ~nd 4,175,175, -~0 - R' - O - Rll~n XIX
wherein R' is ~ residuum of El dihydrlc phenol such ~s blsphenol A, hydroquinone, resorclnol, 4,4-blphenol, 4,4'-dlhydroxydiphenyl su~fone, 4,4'-dihydroxy-3,~' 5,5'-tetr~methyldiphenyl sulfide, 4,4'-dihydroxy-3,3',5,5'-tetr~methyl-dlphenyl sulfone ~nd the llke. R" 1~ a residuum of a benzenoid compound susceptlble to nucleophlllc sromatlc ~ubstleution reac~lons such ~s 4,4'-dichlorodlphenyl sulfone, 4,4'-dlflurobenzo-phenone, ~nd the like. The ~verage v~lue of n 18 from ~b~ut 8 to about 120.
~7~8 Other suitable poly,~rylethers Qre de~crlbed in U.S. P~tent 3,332,209.
Also 3ult~ble ~re p~lyhydroxyether~ of the formuls:
t - R - o - cH2 - cH - CH2tn OH
XX
where R hss the s~me me~ning ~s ~or Formuls XYIII
~nd the ~vera~e v~lue of n 1~ between Hbout 8 snd about 300. Other ~ult~ble thermoplastlcs include poly (c-csprola tone); polybut~dlene;
polybutadlene/~crylonltrlle copolymers, lncludlng those option~lly cont~ining epoxy, vlnyl, ~crylic, methacrylic, amlnei carboxyl, hydroxy, or thlol groups; polyesters, such as poly(butylene terephthalete) and poly(ethylene terephth~late);
polyetherimides ~uch BS the Ultem*resins (obtalned from the General Electric Compcny); polycarbon~te su~h ~s the Lex~n reslns (obtalned from the Genersl Electric Company); scrylonitrile/butadlene/s~yrene copolymers; polyamldes fiuch as nylon 6, nylon 6,6, nylon 6,12, and Trog~mid T (obt~ined from Dynamit Nobel Corpor~tion); poly(~mldelmides) such BS Torlon*
(obtained from Amoco Chemicel Corpo~tion, Naplervllle, ~L); polyolefln~; polyethylene oxlde;
poly(butyl meth~cryl~te); imp~ct-modlfled polystyrene; sulfon~ted polyethylene; poly~ryletes * Tr~demark 6~
~ 8 such ss tho~e derived from blsphenol ~ ~nd l~ophthslic ~nd terephth~llc scld; poly(2,6-dlmethyl phenylene oxide) ~nd lts copolymers; polyvlnyl chlorlde ~nd lt8 copolymer~; poly~cee~
polyphenylene sulflde ~nd the llke.
Poly(vinyl ~cetate) snd copolymers of vinyl acetdte wlth other vinyl ~nd acryllc monomers m~y slso be used. Thermoplastics auch es 13~ profile ~ddltives, for ex~mple, W -40A, m~y ~1BO b~ u8ed.
Also sultabl~ sre vinyl methyl or vlnyl phenyl silicone rubbers such as polymers of the ~ormula -R2S10- whereln up to lOS of the R ~roups ~re ~inyl, the remslnder being either methyl ~nd/or phenyl.
Psrticularly 8U ltable ~re rubber modifiers, such ss but~dlene polymers and but~diene/~crylonitrile copolymers lncluding those option~lly cont~lning termln~l ~nd/or pendent smlne, epoxy, csrboxyl, hydroxyl, thlol, or uns~t~r~ted double bond groups, ~uch as ~crylstes or methscrylstes or vinyls. The~e Rre exempllfied by the Hyc~r Re~c~lve Liquld Polymers ~Ysll~ble from B.F. Goodrich, the 1,2-polybut~dlene resins ~v~ ble from Nippon Soda Co., the polybutsdiene reslns ~vallsble ~rom Arco Chemic~l Co. (~s poly-BD
reslns) and others. Elastome~s such as e~hylene/Acrylic copolymers, exempllfied by the V~m~c*reslns av~ ble from DuPont, end other el~stomerlc polymers ~nd copolymer m~y ~l~o be used. Also suit~ble are the polyester elastomers ~uch as the Vitel*resins tVitel* 307, etc.) vhlch are dvailsble from B.F. Goodrich.
* Trademark r ~ ~
~4V'~
` 26 -~ he preferred thermopl~stics include polysulfones, phenoxy res~ns, polysrylates, the butadlene/~crylonltrile copolymers descr1be~ above and the polyester el2stomer~. Mlxtures of such thermoplsstlc modlfiers m~y Qlso be u~ed.
The ~tructursl flbers which ~re u~Eul ~n thls invention include c~rbon, gr~phi~e, gla~s, ~llicon carbide, poly(benzothl~zole), poly(benzimldszole), polytbenzoxazole), ~lumlnum, tltanlum, boron, ~nd ~rom~tic polysm~de fibers.
These flbers ~re chQracterlzed by a tenslle stren~th f Bre~ter thsn 100,000 psl, ~ tenslle modulus of 8~eater th~n two mill1On psi, ~nd 8 decompositlon temper~ture of 8reater than 200C. The flbers may be used in the form of contlnuous tows (lO00 to 400,000 Eilaments each), woven cloth, whlsXers, choppecl fiber or random mQt. The preferred ~lber~
~re c~rbon flbers, aroms~lc polysmlde fibers, such ~s Kevlar*49 flber (obtained from E.I. DuPont de Nemours, Inc., Wllmlngton, DE), and slllcon c~rblde fibers.
The composltlons of the resin formulstions of ~he lnventlon contsin 1 to 99 wel~ht percent, prefersbly 20-90 percent of the blsmaleimlde; 1 to ~bout 70 perc~nt, preFer~bly 10 to 60 percent of the olefln ether coreactant; 0 - 50 percent of an Qddltlon~l mlxture of cDreact~nts comprlsing molecules wlth one or more smino, epoxy, ~yan~te, vlnyl groups such as -CH=CH~,~C~CH2, or -CH-CH-snd other functlon~litles ~s described ~bove; snd 1 to ~bout 40 percent, preferably 2 to 30 pe~cent of other ~dditlves, 8uch ~s thermoplas~ic poly~ers and other core~ctants.
* Trademark ~ I
- : .
~ J~
AddltionQl component~ ln the compo~itlon lnclude lnltiator~ for vlnyl polymeriz~tion ~uoh ~s di-t-~utyl peroxlde, dicumyl peroxlde, 1,1-~18 ( e -bu~ylperoxy) cyclohexane, 8Z o bls-(isobutyro-nitrile~, t-butyl perbenzoate, ~nd the like. The inlti~tor comprlses from 0 to 3 percent by we~gh~ of ~he total composl~lon.
Inhlbitors for vlnyl polymerl~tlon~ may also be used. They include hydroquinone, ~-butyl hydroquinone, benzoquinone, p-me~hoxyphenol, ~d 4-nltro-m-cresol. Inhlbitors sre present ln ~mounts of from 0 to 2 percent by wei~ht of the total composition.
When 3 structur~l flber is u~ed, the ~mount of flber ln the total compo~ltlon ls between sbout 10 and ,~bout 90 percent by wei~h~, prefer~bly between about 20 to about 85 percent by wei~ht.
Preimpregnated relnforoement may be made from the composltions of this invention by ~ombining the resin formulations wlth a structural fiber.
Preimpregneted relnforcement msy be prepsred by ~everal technlques known ln the art such as wet wlnding or hot melt. In cne ~ethod of makin8 ~mpregnA~ed tow or undirection~l tape, the resln is first coated ~s 8 thin fllm on release pAper. TWo rolls of thls co~ted psper plus sligned tows of carbon flber ~re then pressed together ond p~3sed through a serles of hested rollers to effect wet-out o~ the Elber tows by the resln. The thusly formed prepreg ls then ~llowed to cool ~nd taken up on ~pool.
Compssites may be prep~red by curln~ the prelmpregn~ted reinforcement usln heat ~nd optlonally pressure. V~cuum b~g/Autoclave cures ~ork well wlth these composltions. L~mlnates m3y also be prepared vi~ wet l~y up followed by compression moldln~, resin transfer ~oldlng, or by res~n in~ection, as descrlbed ln Europe~n PA~ent Application 0019149 published November 26, 19aO.
Typic~l cure temperetures are lOO~F to 600F, prefer~bly 1~0F to 490F.
The compositlons of this invention ~ay also be used for fll~ment wind1ng. In thls composite f~bric~tlon process, contlnuous reinforcement in the form of t~pe or tow - either prev~ously ~mpregnAted w~th resin or impregnsted during winding - i~ plsced over a rotQting snd removable form or mandrel in 8 previously determined psttern. Generally ~he sh~pe iS Q surface of revolutlon ~nd cont~lns end closures. When the proper number of l~yers are applied, the wound form ls cured ln sn oven or ~utocl~ve and the mandrel re~oved.
Tscky drsp~ble prepreg c~n be obtained with a wide v~rlety of composltlons. Long prepre~ ~helf llves cQn be obtAlned-typica,Lly one to four weeXs.
The compositions of th~s lnventlon may be used ~s matrlx reslns for composites, hlgh temperature coatlngs, and ~dhesives. ~en relnforced wlth structural fibers, ~hey m~y be used ~s Aircr~t p~rts ~uch as wlng ~klns, wing-to-body falrings, floor psnels, flaps, radomes; 8S
au~omotive parts, ~uch ~s drlve sh~fts, bumpers, snd springs; ~nd QS pressure vessels, tanks snd pipes.
~-~5180 .,, They are ~lso ~ultQble for protectlve ~rmor on mllitary vehlcles ~nd aporting goods applic~tlons such 8s golf ~hsfts, tenni r~cket~, ~nd fl~hln~
rods.
In addltlon to ~tructural flber~, ehe composition mYy ~180 cont~in partlculate fillers such ss talc, micQ, c~lcium carbon~t~, aluminum trlhydrate, glass microb~lloons, phenolic thermospheres, and c~rbon bl~cX. Up to half of the weight structur~l flber in the compositlon ~y be repl~ced by flller. Thlxotropic a~ents ~uch 9S
fumed sllic~ may elso be used.
EXAMPLES
The following e~amples servP to ~l~e ~peçl$1c illustrations of the pr~ctice of th1s inventlon but they are not intended in ~ny way to limlt the ~cope of thls inventlon.
ExsmPle l. PrepsrRtlon of 2-methoxy 4-allyl-1-allyloxybenzene (ally~ ether of ugenol).
A 5 Q 4-neck flssk equlpped with sn overhead stlrrer, addltion funnel, reflux condenser, nltrogen inlet ~nd outlet, arld he~tlng mantle w~s ch~rged with 2 Q n-prop~nol, 656.8 ~ of Eu8enol, ~nd 165.0 8 of freshly opened 30d~u~ hydroxlde pellets. The mixture w~s s~lrred and heated at reflux until the sodlum hydroxlde h~d dlssolved.
400 ml of allyl chlorlde was then slowly added over 20 mlnutes while ~entle reflux was contlnued. The lemon yellow reactlon mlxture ~as then reFluxed An ~ddltlonsl 5 hour~ Qnd st~rred ~t room temperQture overnlght.
~-15180 The preclpit~ted ~odlum chlorlde was removed by filtr~tion and the n-propanol ~s ~tripped under vacuum on ~ rotsry ev~por~tor. The crude product w~s d~luted with 2 Q of ~ethylene chloride ~nd th~t 601ution wsshed twice with w~ter and ~wice wlth brine. The methylene chloride w~s removed under vQcuum on a rot~ry ev~por~tor ~nd the product then filtered through sodlum sulph~te ~nd held undzr v~cuum overnlght. The yleld of liquld dlluent w~s 811 ~ snd the NMR w~s consistent with the expected structure shown below.
~0 CH2C~I=CE12 CH2=CH-CH ~
The bolling polnt of this diluent ~as over 250C t ~tmospheric pressure. The diluent w~s st~ble up to th~t temperQture ~nd, even when cured in the presence of a free r~ldical lnhibitor (see schedule A ~s discussed herl31nbelow), showed only partl~l cure ~nd could not be tested mechanlc~lly.
Ex~mPle_2. Prepar~tion of 4,4~-dl~llyloxydlphenyl-isopropyli.dene (diallyl ether o~ ~isphenol A).
A 3 ~ 4-neck flask equlpped ~s in Ex~mple l was ch~r~ed wlth 1 Q n-prop~nol, 22B ~
of Bisphenol A, ~nd B2.5 g of freshly opened sodium hydroxlde pellets. The mlxture WBS stirred and he~ted ~t reflux untll the ~odlum hydroxide h~d dlssolved ~nd 200 ml ~f Qllyl chlor~de was then added ~lowly whlle gentle re~lux w~s continued. The ........ , . ,. ., -re~ctlon m~xture w~s refluxed an ~ddltlonsl 6 hours and then stlrred ~t ro~m tempersture oYernl~ht.
The preclpit~ted sodlum chloride ~as removed by filtratlon ~nd the n-propanol w~s str~pped under v~cuum on ~ rotsry ev~porQtor. The crude product w~s dlluted with 1 ~ of methylene chlorlde ~nd thst solution w~shed ~wlce with w~ter And once wlth brine. The methylene chlorlde was strlpped OR ~ rot~ry ev~porRtor ~nd the product flltered through sodlum ~ulphate ~nd held under vacuum overnlght. The yleld was 148 8 ~nd the NMR
W8S conslstent with the expected structure shown belo~.
c~2=CHCH2{)4~C~o_CH2CH~12 The bolling point of this dlluent was over 250C ~t atmospherlc pressure. The dlluent W8S
stsble up to th~t temperature ~nd, even when cured in the presence of ~ free radic~l inltlator (cure schedule A ~s discussed hereinbelow), showed only p~rtl~l cure ~nd could not be tested mechsnlc~lly.
Example 3. Prepara~ion of me~a-dlallyloxybenzene.
A 3 Q 4-neck fl~sk equlpped as ln Exsmple 1 W85 char~ed wlth 1.5 Q
dlmeehylform~mide, 110.1 8 re&orcinol, ~nd 345 ~ of ~nhydrous potasslum c~rbon~te. The mlxeure ~8S
~tirred and hested ~t 100C untll most of the csrbonate w~s in ~oluti~n and 20Q ml of ellyl ~-151~0 - ..
.. .
~'~ 7 ~
- 3~ -chlorlde w~s then ~dded over about 1 hour. Heatlng w~s continued for 5.5 more hour~ snd the ~ct~on ~s then ~tlrred overnl~ht at ro~m temperature.
The resction mlxture w~s dlluted wlth 1 ~
of methylene rhlorlde snd th~t solutlon W8S washed ~ix tlmes with brlne. The methylene chlorlde ~olution w~s ~hen flltered thrDugh sodlum ~ulphate and the methylene chlorlde was removed under vacuum on a rot~ry ev~por~tor. The llquld residue WBS held under vacuum overnlght. The yield w~s 157 ~ ~nd ~he NMR w~s consi~ent with ~he expected fitructure ahown bels~ .
CH2~cH2~ 0~2CH¢H2 The boillng polnt of this diluent was over 250C ~t stmosphPric pressure. The diluent w~s stable up to thst temper~ture and, sven when cured ln the presence of a free r~dical inl~i~tos (cure schedule A BS d1scussed hereinbelow), ~howed only p~rtial cure and could not ~e tested mechanlc~lly.
Ex~mPle 4. Prep~ration of 1,3-dlallyloxy-2-methyl-benzene.
A 3 Q 4-neck fl~sk equlpped 8S ln Example 1 W8S ch~rged with ~.5 Q of dimethyl ~cet~mide, 124 g of 2-me~hylresorcinol, and 345 g of ~nhydrous pot~ssium carbonRte~ The mixeure was stlrred and heated to lOODC. A 200 ml`chsr~e of ~llyl chlorlde WHS then ~dded over 1 hr. ~eatin8 and ~tirrin~ were con~lnued for 5.5 hrs. The mlxtur~ ~s ehen ~tirræd snd let cool overni~he.
, : . ~ , .
, ~ 7 The resctlon mlxture WBS dlluted wlth 2 ~
of methylene ehloride and th~t ~olutlon ~as ~hed with four 2 ~ portlons of water, twice wlth dllute ~.25M) pot~sslum csrbonste, ~nd four 2 ~ portion~
of brine to glve a light ~old solution. The 801utlon was flltered through ~odlum 6ulf~te snd the methylene hlorlde was then removed on a rot~ry evaporator to glve 191 ~ of ~ liquld product. The NMR was consistent wlth the expected structure ~hown belo~.
~2~2~-~2~2 The boillng point of this diluent w~s over 250G.
The diluents prepsred ln Ex. 1-4 were ~11 odor-free or possessed A mlld odor. All had bo11ing poin~s of over 250C and were ~table, showing no signs of gellHtlon up to thst temperature, even ln the 8bsence of lnhlbltors.
ExsmPle 5. Bismslelmlde/dlluent mixture.
A mlxture of 6.6 g of SED-M bl~meleimide (4,4'-bls(3-m~leimldophenoxy) dlphenyl sulfone) Qnd 3 4 8 of the dlsllyl ether of Bi~phenol A (product in Example 2) was blended on a rot~ry ev~p~rstor ~t 125C untll homogeneous. It was mixed and hel~
under vacuum sn ~ddlt1onsl 10 mlnutes for de-g~sslng ~nd then poured into ~ small casting frfime formed from glsss pl~tes and B l/16" Teflon sp~cer gesXet.
* Trademark 7 ~
The clear mixture WAS cu~ed ~ccor~lng t~ ~he followln~ schedule:
25~C~ 79C ~t- 1.5~/min. Hold 2 hr~.
7~C~ 177C ~t 1.5/mln. Hold 4 hr~.
177C~ 246C ~t l~/min. Hold 4 hrs.
246~C ~ 25C at 1.5/min.
The cured c~sting was found to h~ve ~ Tg (pe~k of damping curve) of 240C (DMA sc~n st 5C/min.~ and absorbed 1.6S wster dur~ng ~ 2-week soak at 160F.
ExsmPles 6-20.
The procedure of Exsmple 5 w~s repeated using the ~ngredients llsted ~n T~ble I. The T~ nnd wR~er absorption d~t~ for the cured m~terials is slso listed in T~ble I~
In some cases, an ~ltern~te cure schedule w~s used, Qnd det~lls of the cure schedules ~re given in the T~ble notes. Some resins were mixed at 140C lnste~d of 125~C.
D~lSlflO
'7~
TABLE I
Formul~tlon C~stings (Bi~mslelm1de/D~luent) E~ Bis~ lmldaDllu~nt Cur~ ~ ~31120 Abl;orbi~d -6.6 SED~ll 3.d D~aA~ A 245 2.1 6 7.~ SEDMI 2.6 EC07 A ~ 2.6 7 7.6 SEOMI 2.4 DERq ~ 2B5 2.1 8 6.5 B~P2 ~.5 DBA ~ 225 ~.5 9 6.5 B~2 i.5 DEBA B 222 ~. l 7.4 BA~P2 2.6 DEBA B 2~0 2.6 Il 7.1 ~pp2 2.6 EC0 A ~IC 2.6 12 7.d B~PP 2.6 DAMR9 A 270 13 7.0 BA~ ~.0 EC0 A 265 Z.l 14 6.9~4 ~.l EC0 ~ ~20 5.
5.4 CoMP.3535 4.6 BEBA A 2 16 6.2 C~lP.~5~5 ~.B DEBA 8 2~0 4.~
17 6.2 OO~P.3535 3.B EC~ A ~ 1.7 18 6.2 co~P.35~5 ~ C0 C ~5 ~1.0 19 6.2 co~P.3535 ~.B EC0 D ~60 4.1
17 6.2 OO~P.3535 3.B EC~ A ~ 1.7 18 6.2 co~P.35~5 ~ C0 C ~5 ~1.0 19 6.2 co~P.3535 ~.B EC0 D ~60 4.1
6.~ P. 35~5 3.2 EC0 C ~70 4.4 21 6.2 CO~ 53 ~.9 DAMR 1~ 310 Table I Notes 1. 4,4'-bls(3-maleimidophenoxy) diphenyl ~ulfone.
2. 4,4'-bis(4-maleim~dophenoxy) dlphenyl isopropylidene.
3.o~,~ -bis(4-msleimidophenDxy)-met~-dllsopropyl-benzene.
4. 1,3-bls(4-maleimidophenoxy)benzene.
5. Compimlde 353. A blsmalelmide mixture svsilQble commercially from Boots-Technochemle.
6. Dlallyl ethPr of bicphenol ~ (ExRmple 2).
2. 4,4'-bis(4-maleim~dophenoxy) dlphenyl isopropylidene.
3.o~,~ -bis(4-msleimidophenDxy)-met~-dllsopropyl-benzene.
4. 1,3-bls(4-maleimidophenoxy)benzene.
5. Compimlde 353. A blsmalelmide mixture svsilQble commercially from Boots-Technochemle.
6. Dlallyl ethPr of bicphenol ~ (ExRmple 2).
7. Allyl ether of Eugenol (Example l).
8. Di~llyl ether oF resorclnol (Example 3~.
9. Dl~lly~ ether of 2~methylresorclnol (Example 4).
10. 2 week sosk in 160F water.
, " ' ' ' ' ~'7 Cure Schedules ~.C~
. 25 79 ~t 1.5lmln. 9 hold 2 hr~.
79 177 ~t 1.5~/min., hold 4 hrs.
177 ~ 246 at 1/min., hold 4 hrs.
246 > 25 ~t 1.5~1min.
. 25 177 ~t 1.5/min., hold 6 hrs.
177 ~ 246 Bt 1/min., hold 4 hrs.
246 ~ 25 ~t 1.5/mln.
C. 25 79 at 1.5/mln., hold 2 hrs.
79 177 ~t 1.5~/min.p hold 4 hrs.
177 1 235 ~t 1lmin., hold 4 hrs.
235 25 st 1.5/min.
D. 25 ~ 79 Bt 1.5lmin., hold 2 hrs.
79 ~ 177 ~t 1.5lmln., hold 4 hr 177 220 ~t l~/min., hold 4 hrs.
220 ~ 25 ~t 1.5/min.
Examples 18, 19 Qnd 20 lllustrete the very high Tg values which c~n be obtQlned under reduced post cure temper~tures wlth one of the diluents of this invention.
Example 22-37.
The procedure of ExRmple 5 (~ome ex~mples were mixed ~t 140C lnstesd of 125~C) WQS repe~ted usin~ ~he lngredients li~ted ln Tsble II. In these Ex~mples, the bssic bism~leimlde/diluent mixture w~s modlfied by the Qddltion of varlous cy~ns~e e~t~r resln modlfiers.
~-15~80 :, .,. ~' ' 3'~3 G
L C~ ~ ~ O O r~ O ~
~ -- ~i N ~ ~ ~`J ~ ,, I N ~ N ~I N ~ ~ ~ u .9i ,_ C
X ,__ V ~ o_, ô
-tJ ~ NNNNNNNNNNN~NNN~
n o o Q o o, e~ o, ~D ~ .
X -- ~
YQ~OOO~OQO~QOOCOO - _~_C
~Q~NG~G~-C~OOO ~C~
C Dl -NNNNNNNNN~NNN~N C _~
~ S ~ S S ~ -- ~ ~ ~., C
~OO~NN~OO~NO ~ U ~
. ~ O ~ ~ - I V æ
Z
~ ~ ~n ~ ~ C
f NNNN~N~N~N~ ~ _ N ~
~ . :" ' "' '' . :
, Ex~mple 38 - 49.
The procedure of Ex~mple 5 w~s repe~t~d ~lng the lngredients in T~ble III. In thes~
examples the b~sic blssn~lel~lde ~ixture W~8 m~dlfi~d by the ~ddition of the thermopl~stic mlxtures.
"' .
. .
4~3 t~ D t~ ~ ~ e~ t~ s ~ D ~ D
~J r Z ~ ~ t~J I tl I ~ I I I I , o E ~ Z
~D E ~ t~,~, c ._ ~ tD O tD
,~ ~ ~ t~ <t <r ~ a ~ .~ D ~ ~~ O
n .", ", 5 IDID
O ~ t t~ ~ tD t Q Q tD t ID ~ ~ c r D = _ ~
e ~ -- -- o o -- ~ ~ ~ ~ ~ _ ~' ~D . _ _ E -- ,0 ~7 _ ._ L O~D1~ Vl tO ,~ o O Q ~ ~O~ t~ tJ ~ c L ~ t~ C
Z -- t ~ t~ ~ t~ C ~ L ~D _ L
~-- C ~D C Vl u C r C~ ~
~D ~e _ c~ D ~
c ~ ..... .~o _ e o tD o u i~ t~ <~ ~ c c ~ ~ , g g ~ E IE t o ~1 ~ O ;D O
v ~ r~ Ch ~ N UU- O O O O Ir) O ~D C7 ~ 10 L tD ~-- ti ~D ~ ~D ro a ~ D t~i ~o -- t~ t~ ~ ~ tD ~ tD -- ~
~D u O ~ ~ C /~ S
~0 ~ t~ ~ ~D O~ _ _ t~ t~
' Examples 44, 45~ 4~ ~nd 47 illustrate the ~Qrtlculer ~dvant~ge of ECO In providlng proce~slble teslns wlth hlgh levels ~i.e., ~10~) of rubbe~ modifier~.
The low vi~co~ity of ECO 18 very useful ln formulations of thls type while still providing hlgh TX's and thermAl st~blllty before ~nd after cure.
ExamPles 50-54.
The procedure of Exemple 5 was repe~ted using the ingredients li~ted ln T~ble IV. In these ex~mples the bi.~mslelmide/diluent mixture w~s modified by the sddition of 2 thermoplRstlc polymer plus a cysn~te ester compound.
-~ 2~
L ~ ~ O N O
~_ ;~ t`,l N N N
C ID
L.J ,~
Z Z Z C~
~-L~J C~
J u~ o a o o ~ e~ -- o ~ ~r - ~ ~
I ~1 N N I~J
~ a o o _ _ _ _ Z
~6 ~ O ~, C~ ~o~ o Z _ ~ "~
O _ N N N N --~ O
~_ ~ ~n _ ' ._ t- ~ E~ ~
~ ~ O` O~ ~ _ -~1 ~
-'''.:
.~ ' .' ''~
.
.,, ' ' ~
~ '~ " '~ ' ' , ~.~7'~
.
Ten~ile prop~rties were obt~ined ~ccordlng to ASTM D-638 on lsr~er oastlng~ (1/8" thick) ~de from some of the ~bove formulstion~. These ~re listed ln Tnble V.
TABLE V
Tensile Tensile ExRmple T~Dc) Stren~th Modulus El~on~tlon 44 -360 6.4 ksl 326 ksl 2.8 41 -320 6.7 X~l 459 ksl 1
, " ' ' ' ' ~'7 Cure Schedules ~.C~
. 25 79 ~t 1.5lmln. 9 hold 2 hr~.
79 177 ~t 1.5~/min., hold 4 hrs.
177 ~ 246 at 1/min., hold 4 hrs.
246 > 25 ~t 1.5~1min.
. 25 177 ~t 1.5/min., hold 6 hrs.
177 ~ 246 Bt 1/min., hold 4 hrs.
246 ~ 25 ~t 1.5/mln.
C. 25 79 at 1.5/mln., hold 2 hrs.
79 177 ~t 1.5~/min.p hold 4 hrs.
177 1 235 ~t 1lmin., hold 4 hrs.
235 25 st 1.5/min.
D. 25 ~ 79 Bt 1.5lmin., hold 2 hrs.
79 ~ 177 ~t 1.5lmln., hold 4 hr 177 220 ~t l~/min., hold 4 hrs.
220 ~ 25 ~t 1.5/min.
Examples 18, 19 Qnd 20 lllustrete the very high Tg values which c~n be obtQlned under reduced post cure temper~tures wlth one of the diluents of this invention.
Example 22-37.
The procedure of ExRmple 5 (~ome ex~mples were mixed ~t 140C lnstesd of 125~C) WQS repe~ted usin~ ~he lngredients li~ted ln Tsble II. In these Ex~mples, the bssic bism~leimlde/diluent mixture w~s modlfied by the Qddltion of varlous cy~ns~e e~t~r resln modlfiers.
~-15~80 :, .,. ~' ' 3'~3 G
L C~ ~ ~ O O r~ O ~
~ -- ~i N ~ ~ ~`J ~ ,, I N ~ N ~I N ~ ~ ~ u .9i ,_ C
X ,__ V ~ o_, ô
-tJ ~ NNNNNNNNNNN~NNN~
n o o Q o o, e~ o, ~D ~ .
X -- ~
YQ~OOO~OQO~QOOCOO - _~_C
~Q~NG~G~-C~OOO ~C~
C Dl -NNNNNNNNN~NNN~N C _~
~ S ~ S S ~ -- ~ ~ ~., C
~OO~NN~OO~NO ~ U ~
. ~ O ~ ~ - I V æ
Z
~ ~ ~n ~ ~ C
f NNNN~N~N~N~ ~ _ N ~
~ . :" ' "' '' . :
, Ex~mple 38 - 49.
The procedure of Ex~mple 5 w~s repe~t~d ~lng the lngredients in T~ble III. In thes~
examples the b~sic blssn~lel~lde ~ixture W~8 m~dlfi~d by the ~ddition of the thermopl~stic mlxtures.
"' .
. .
4~3 t~ D t~ ~ ~ e~ t~ s ~ D ~ D
~J r Z ~ ~ t~J I tl I ~ I I I I , o E ~ Z
~D E ~ t~,~, c ._ ~ tD O tD
,~ ~ ~ t~ <t <r ~ a ~ .~ D ~ ~~ O
n .", ", 5 IDID
O ~ t t~ ~ tD t Q Q tD t ID ~ ~ c r D = _ ~
e ~ -- -- o o -- ~ ~ ~ ~ ~ _ ~' ~D . _ _ E -- ,0 ~7 _ ._ L O~D1~ Vl tO ,~ o O Q ~ ~O~ t~ tJ ~ c L ~ t~ C
Z -- t ~ t~ ~ t~ C ~ L ~D _ L
~-- C ~D C Vl u C r C~ ~
~D ~e _ c~ D ~
c ~ ..... .~o _ e o tD o u i~ t~ <~ ~ c c ~ ~ , g g ~ E IE t o ~1 ~ O ;D O
v ~ r~ Ch ~ N UU- O O O O Ir) O ~D C7 ~ 10 L tD ~-- ti ~D ~ ~D ro a ~ D t~i ~o -- t~ t~ ~ ~ tD ~ tD -- ~
~D u O ~ ~ C /~ S
~0 ~ t~ ~ ~D O~ _ _ t~ t~
' Examples 44, 45~ 4~ ~nd 47 illustrate the ~Qrtlculer ~dvant~ge of ECO In providlng proce~slble teslns wlth hlgh levels ~i.e., ~10~) of rubbe~ modifier~.
The low vi~co~ity of ECO 18 very useful ln formulations of thls type while still providing hlgh TX's and thermAl st~blllty before ~nd after cure.
ExamPles 50-54.
The procedure of Exemple 5 was repe~ted using the ingredients li~ted ln T~ble IV. In these ex~mples the bi.~mslelmide/diluent mixture w~s modified by the sddition of 2 thermoplRstlc polymer plus a cysn~te ester compound.
-~ 2~
L ~ ~ O N O
~_ ;~ t`,l N N N
C ID
L.J ,~
Z Z Z C~
~-L~J C~
J u~ o a o o ~ e~ -- o ~ ~r - ~ ~
I ~1 N N I~J
~ a o o _ _ _ _ Z
~6 ~ O ~, C~ ~o~ o Z _ ~ "~
O _ N N N N --~ O
~_ ~ ~n _ ' ._ t- ~ E~ ~
~ ~ O` O~ ~ _ -~1 ~
-'''.:
.~ ' .' ''~
.
.,, ' ' ~
~ '~ " '~ ' ' , ~.~7'~
.
Ten~ile prop~rties were obt~ined ~ccordlng to ASTM D-638 on lsr~er oastlng~ (1/8" thick) ~de from some of the ~bove formulstion~. These ~re listed ln Tnble V.
TABLE V
Tensile Tensile ExRmple T~Dc) Stren~th Modulus El~on~tlon 44 -360 6.4 ksl 326 ksl 2.8 41 -320 6.7 X~l 459 ksl 1
11 310 7.2 ksi 463 ksi 1.9~
28 ~65 7.2 k~i 495 ksi 1.7S
These properties show ~n sttr~ctlve bslsnce of ~oughness and high T8 vQlues.
ExamPle 55 - "B-~t~ln~" of bi~malelmlde~diluent Mlxture.
A mlxture of 5.58 g Complmlde~353 blsmalelmide, 3.42 g EC0 diluent, ~nd 1.0 ~ VT~ X22 llquld rubber (Goodrlch Chemlcal Co.) WA8 blended on a rot~ry evapor~tor ~t 12~C. The low vi8c08ity mlxture was perlodicslly ~smpled ~nd tested for fllm properties by drawlng down a 1 mll film on rele~se paper.
Ten mlnutes sfter mlxln~ the s~mple Ellm WAS very tscky ~nd showed lmmedlate retlculatlon or "beadlng". Such ~ilms sre gener~lly dlfficult t~
use ~n the prepara~lon of cflrbon fiber prepreg products. After 30 mlnuteQ there was llttle change ln the ssmpled fllm. After the mlxture h~d been heated 1.5 hr., the degree Qnd ~peed o~ retlcul~tlon decreased and the re~in mixture was ~ htly ~ore * Trademark D-1$180 .2~
viscous. AdditlonRl ~mples ~t 30 ~inute in~ervals continued to show improvements ln ~llm prop~rties until ~fter ~bout 2.5 hrs. the film showed only small pinholes ~fter Rtsnding. The r~sin ~8S ~l~her ln vlscosity but 5till fluid. The film showed t~ck ~nd wcs ~ultable for preprsg fabricaeion.
Ex~mPle 56 - Preparation of C~rbon F~ber Com~osite A mixture of 1120 B Complmide 353 bism~lelmlde, 680 g ECO, 200 8 VTBN 1300X22, ~nd 40 g Cab-o-Sil (N-70-TS, hydrophobic) was stirr~d ~e 125C untll ~ fllm sample withdr~wn showed ~ood fllm properties snd little or no retlcul~tion. A tat~l heatlng period of about 7 hours was used.
The resin mixture w~s coated on o differential sillcone-coated release psper and then fabric~lted viu stand~rd prepregging procedures lnto A carbon flber prepreg product using T-40 fibers (12K) ~rom Union Carblde Corporstion~ An ed8e delflmin~tlon test composite, I+ 252/90]~, w~s f~bricated from this prepreg and gave an sversge edge del~mination strength o~ 21 ksi. The ~g of the resin cured under slmllsr condltions w~s -350C.
D-lSlB0 ... ` ~..
..
'
28 ~65 7.2 k~i 495 ksi 1.7S
These properties show ~n sttr~ctlve bslsnce of ~oughness and high T8 vQlues.
ExamPle 55 - "B-~t~ln~" of bi~malelmlde~diluent Mlxture.
A mlxture of 5.58 g Complmlde~353 blsmalelmide, 3.42 g EC0 diluent, ~nd 1.0 ~ VT~ X22 llquld rubber (Goodrlch Chemlcal Co.) WA8 blended on a rot~ry evapor~tor ~t 12~C. The low vi8c08ity mlxture was perlodicslly ~smpled ~nd tested for fllm properties by drawlng down a 1 mll film on rele~se paper.
Ten mlnutes sfter mlxln~ the s~mple Ellm WAS very tscky ~nd showed lmmedlate retlculatlon or "beadlng". Such ~ilms sre gener~lly dlfficult t~
use ~n the prepara~lon of cflrbon fiber prepreg products. After 30 mlnuteQ there was llttle change ln the ssmpled fllm. After the mlxture h~d been heated 1.5 hr., the degree Qnd ~peed o~ retlcul~tlon decreased and the re~in mixture was ~ htly ~ore * Trademark D-1$180 .2~
viscous. AdditlonRl ~mples ~t 30 ~inute in~ervals continued to show improvements ln ~llm prop~rties until ~fter ~bout 2.5 hrs. the film showed only small pinholes ~fter Rtsnding. The r~sin ~8S ~l~her ln vlscosity but 5till fluid. The film showed t~ck ~nd wcs ~ultable for preprsg fabricaeion.
Ex~mPle 56 - Preparation of C~rbon F~ber Com~osite A mixture of 1120 B Complmide 353 bism~lelmlde, 680 g ECO, 200 8 VTBN 1300X22, ~nd 40 g Cab-o-Sil (N-70-TS, hydrophobic) was stirr~d ~e 125C untll ~ fllm sample withdr~wn showed ~ood fllm properties snd little or no retlcul~tion. A tat~l heatlng period of about 7 hours was used.
The resin mixture w~s coated on o differential sillcone-coated release psper and then fabric~lted viu stand~rd prepregging procedures lnto A carbon flber prepreg product using T-40 fibers (12K) ~rom Union Carblde Corporstion~ An ed8e delflmin~tlon test composite, I+ 252/90]~, w~s f~bricated from this prepreg and gave an sversge edge del~mination strength o~ 21 ksi. The ~g of the resin cured under slmllsr condltions w~s -350C.
D-lSlB0 ... ` ~..
..
'
Claims (11)
1. Resin formulations comprising:
(a) a bismaleimide; and (b) at least one or more of a reactive diluent which may be described by the following general formula:
where Z = O or S, and where R = -CH=CH2, -CH2CH=CH2, -CH=CHCH3, n ? 1, m = 0 to 2, m + n ? 2 Ar = and where Ar may be substituted with alkyl, alkoxy, halogen, and other non-reactive groups in which X = alkylidene, aryl, arylalkylidene, O, S, SO2, CO, - ? - O -, - ? - NH -, - O(CH2)nO -.
(a) a bismaleimide; and (b) at least one or more of a reactive diluent which may be described by the following general formula:
where Z = O or S, and where R = -CH=CH2, -CH2CH=CH2, -CH=CHCH3, n ? 1, m = 0 to 2, m + n ? 2 Ar = and where Ar may be substituted with alkyl, alkoxy, halogen, and other non-reactive groups in which X = alkylidene, aryl, arylalkylidene, O, S, SO2, CO, - ? - O -, - ? - NH -, - O(CH2)nO -.
2. The resins as defined in claim 1 where the reactive diluent is 2-methoxy-4-allyl-1-allyloxybenzene,
3. The resins as defined in claim 1, where the reactive diluent is 4,4-diallyloxydiphenyliso-propylidene,
4. The resins as defined in claim 1, where the reactive diluent is meta-diallyloxybenzene,
5. The resins as defined in claim 1, where the reactive diluent is 1,3-diallyloxy-2-methylbenzene,
6. The resins as defined in claim 1, in which a mixture of reactive diluents is used.
7. The resins as defined in claim 1, in which a mixture of bismaleimides is used.
8. The resins as defined in claim 1 which includes at least one additional coreactant selected from the group consisting of epoxy resins, aromatic diamines, N-vinyl-2-pyrrolidinone, N-vinyl caprolactam, ethylene glycol dime-thacrylate, diethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacry-late, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythri-tol tetramethacrylate, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate and its isomers, tetraallyl pyromellitate, o,o'-diallyl bisphenol A, Eugenol, triallyl trimellitate, divinyl benzene, dicyclopentadienyl acry-late, dicyclopentadienyl-oxyethyl acrylate, vinylcyclohex-ene monoepoxide, 1,4-butanediol divinyl ether, 1,4-dihydroxy-2-butene, styrene, alpha methyl styrene, chlorostyrene, p-phenylstyrene, p-methylstyrene, t-butyl-styrene, phenyl vinyl ether, unsaturated polyesters, vinyl ester resins, and a compound containing one or more cya-nate ester groups or a prepolymer prepared therefrom.
9. The resins as defined in claims 1 or 8 which con-tains a thermoplastic polymer selected from one or more of polyesters, polyester elastomers, diene rubbers, nitrile rubbers, polyaryl ethers and polysulfones.
10. A composite comprising a resin of claims 1, 8 or 9 and a structural fiber.
11. The resins as defined in claim 1 whexein Ar has at least one substituent selected from the group consisting of:
alkyl, alkoxy, halogen, and other non-reactive groups in which X = alkylidene, aryl, arylalkylidene, O, S, SO2, CO, - ? - O -, - ? - NH -, - O(CH2)nO - ,
alkyl, alkoxy, halogen, and other non-reactive groups in which X = alkylidene, aryl, arylalkylidene, O, S, SO2, CO, - ? - O -, - ? - NH -, - O(CH2)nO - ,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88572386A | 1986-07-15 | 1986-07-15 | |
| US885,723 | 1986-07-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1274048A true CA1274048A (en) | 1990-09-11 |
Family
ID=25387569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000534639A Expired - Fee Related CA1274048A (en) | 1986-07-15 | 1987-04-14 | Bismaleimide formulations containing olefinic ether modifiers |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4853449A (en) |
| EP (1) | EP0253600B1 (en) |
| JP (1) | JPS6323913A (en) |
| CA (1) | CA1274048A (en) |
| DE (1) | DE3775295D1 (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166290A (en) * | 1987-11-30 | 1992-11-24 | Mitsubishi Rayon Co., Ltd. | Resin composition for composite material |
| WO1989005315A1 (en) * | 1987-11-30 | 1989-06-15 | Mitsubishi Rayon Co., Ltd. | Resin composition for composite material |
| US4876325A (en) * | 1988-04-28 | 1989-10-24 | Allied-Signal Inc. | Polyimide resin from bis-imide, polyphenol and dicyandiamide |
| JPH0618835B2 (en) * | 1988-09-27 | 1994-03-16 | 昭和高分子株式会社 | Curable resin composition |
| EP0363524A1 (en) * | 1988-10-14 | 1990-04-18 | Hercules Incorporated | Bismaleimide compositions containing high glass transition temperature and soluble reactive oligomers and composites prepared therefrom |
| JPH0670101B2 (en) * | 1988-11-28 | 1994-09-07 | 三井東圧化学株式会社 | Thermosetting resin composition |
| US5013804A (en) * | 1989-04-14 | 1991-05-07 | Ciba-Geigy Corporation | Curable mixtures containing a bismaleimide and a propenyl compound |
| DE3912532A1 (en) * | 1989-04-17 | 1990-10-18 | Basf Ag | HEAT-CURABLE BISMALEINIMID RESIN |
| DE3929386A1 (en) * | 1989-09-05 | 1991-03-07 | Basf Ag | HEAT-CURABLE BISMALEINIMID RESIN |
| ES2069260T3 (en) * | 1990-05-18 | 1995-05-01 | Ciba Geigy Ag | NEW RETICULABLE COMPOSITIONS. |
| US5359020A (en) * | 1990-05-22 | 1994-10-25 | Ciba-Geigy Corporation | Hardenable compositions comprising bismaleimides, alkenylphenols and phenol diallyl ethers |
| US5132778A (en) * | 1990-09-17 | 1992-07-21 | Motorola, Inc. | Transfer molding compound |
| NL9002758A (en) * | 1990-12-14 | 1992-07-01 | Stamicarbon | ENDLESS ARTICLES OF THERMO-HARDONABLE MONOMERS. |
| EP0501587A1 (en) * | 1991-02-28 | 1992-09-02 | Shell Internationale Researchmaatschappij B.V. | Bisimide resin processing |
| US6034194A (en) * | 1994-09-02 | 2000-03-07 | Quantum Materials/Dexter Corporation | Bismaleimide-divinyl adhesive compositions and uses therefor |
| US7645899B1 (en) | 1994-09-02 | 2010-01-12 | Henkel Corporation | Vinyl compounds |
| US6852814B2 (en) * | 1994-09-02 | 2005-02-08 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| US6960636B2 (en) | 1994-09-02 | 2005-11-01 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| ES2164926T3 (en) * | 1995-11-13 | 2002-03-01 | Cytec Tech Corp | THERMOENDURECIBLE POLYMERS FOR APPLICATIONS IN ADHESIVES AND COMPOSITE MATERIALS. |
| US20030055121A1 (en) * | 1996-09-10 | 2003-03-20 | Dershem Stephen M. | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| CN100447214C (en) * | 2001-05-22 | 2008-12-31 | 株式会社普利司通 | Adhesive composns. and method for bonding to rubber |
| CN101454502B (en) * | 2006-04-28 | 2012-12-12 | 东邦泰纳克丝欧洲有限公司 | Carbon fiber |
| US8034442B2 (en) * | 2007-03-29 | 2011-10-11 | Toho Tenax Co., Ltd. | Fiber-reinforced prepreg and composite material obtained from the same |
| WO2013030103A1 (en) * | 2011-08-26 | 2013-03-07 | Basf Se | Process for producing moldings |
| TWI502786B (en) | 2012-12-21 | 2015-10-01 | Ind Tech Res Inst | Modified maleimide oligomers for battery and compositions containing the oligomers |
| EP2978794B1 (en) | 2013-03-28 | 2017-05-03 | Evonik Degussa GmbH | Curable mixtures based on xylylene bismaleimide |
| JP6080160B2 (en) * | 2013-04-30 | 2017-02-15 | 明和化成株式会社 | Reactive diluent |
| WO2018098830A1 (en) * | 2016-12-03 | 2018-06-07 | 苏州大学张家港工业技术研究院 | Flame-retardant bismaleimide resin and preparation method thereof |
| KR102554568B1 (en) * | 2017-01-18 | 2023-07-11 | 동우 화인켐 주식회사 | Photocurable composition and photocurable layer formed from the same |
| CN114502695A (en) * | 2019-10-07 | 2022-05-13 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN114249896A (en) * | 2021-12-16 | 2022-03-29 | 兰溪聪普新材料有限公司 | Allyl-terminated aryl sulfone ether polymer and preparation method thereof |
| CN114276546B (en) * | 2022-01-18 | 2023-07-07 | 四川泸天化创新研究院有限公司 | Allyl polysulfone containing carboxyl side group and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298720A (en) * | 1979-07-23 | 1981-11-03 | Mitsui Toatsu Chemicals Incorporated | Thermosetting resin composition from maleimide compound and alkenyl phenol |
| US4654407A (en) * | 1985-08-02 | 1987-03-31 | Amoco Corporation | Aromatic bismaleimide and prepreg resin therefrom |
| US4689378A (en) * | 1985-12-16 | 1987-08-25 | Ciba-Geigy Corporation | Stable imide-containing composition from diamino phenyl indane-bis-maleimide and alkenyl phenol |
-
1987
- 1987-04-14 CA CA000534639A patent/CA1274048A/en not_active Expired - Fee Related
- 1987-07-13 EP EP87306163A patent/EP0253600B1/en not_active Expired
- 1987-07-13 DE DE8787306163T patent/DE3775295D1/en not_active Expired - Fee Related
- 1987-07-14 JP JP62174028A patent/JPS6323913A/en active Pending
-
1988
- 1988-01-07 US US07/142,670 patent/US4853449A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0253600A3 (en) | 1989-06-21 |
| EP0253600A2 (en) | 1988-01-20 |
| EP0253600B1 (en) | 1991-12-18 |
| JPS6323913A (en) | 1988-02-01 |
| US4853449A (en) | 1989-08-01 |
| DE3775295D1 (en) | 1992-01-30 |
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